Process for producing cycloolefin addition polymer

ABSTRACT

A process for producing a cycloolefin addition polymer in which one or more cycloolefin monomers can be (co)polymerized by addition polymerization with a small palladium catalyst amount to produce a cycloolefin addition (co)polymer while attaining high catalytic activity. The process for cycloolefin addition polymer production is characterized by addition-polymerizing one or more cycloolefin monomers comprising a cycloolefin compound represented by a specific formula in the presence of a multi-component catalyst comprising (a) a palladium compound and (b) a specific phosphorus compound.

TECHNICAL FIELD

The present invention relates to a process for producing a cycloolefinaddition polymer. More particularly, the invention relates to a processfor producing a cycloolefin addition polymer in which one or morecycloolefin compounds are addition-polymerized in the presence of aspecific catalyst comprising a palladium compound having excellentpolymerization activity to produce a cycloolefin addition polymer thatis preferably used for optical materials and the like.

BACKGROUND ART

With demands for lightening, miniaturizing and densification,substitution of optically transparent resins for inorganic glasses hasbeen advanced recently in fields of optical parts, such as lenses andsealing materials, and liquid crystal display element parts, such asback lights, light guide plates, substrates for TFT and touch panels,where inorganic glasses have been heretofore employed. As the opticallytransparent resins, addition polymers of norbornene(bicyclo[2.2.1]hept-2-ene) type having features of high transparency,high heat resistance and low water absorption properties have been paidattention.

Further, as transparent resins having, in addition to the abovefeatures, small coefficient of linear expansion, excellent thermaldimensional stability, excellent chemical resistance and excellentadhesion to other materials, addition polymers of norbornene(bicyclo[2.2.1]hept-2-ene) and cycloolefins having a hydrolyzable silylgroup and their crosslinked products have been proposed (see patentdocument 1).

Addition polymers of cycloolefins such as norbornene have been obtainedby addition polymerization of cycloolefin monomers by the use ofcatalysts using compounds of transition metals such as Ni, Pd, Ti, Zrand Cr (see, e.g., non-patent document 1)

Addition copolymers of cycloolefin compounds having a polar substituentin the side chain and non-polar cycloolefin compounds are useful ascopolymers not only having excellent heat resistance and transparencybut also being capable of crosslinking to improve adhesion properties,dimensional stability and chemical resistance, and as polymerizationcatalysts for obtaining these copolymers, single complexes of latetransition metals, such as Ni and Pd, or multi-component catalystscontaining Ni or Pd compounds have been mainly employed (see patentdocuments 1 and 2, non-patent documents 2 to 11).

Of these catalysts, the multi-component catalysts are industriallyemployed more frequently rather than the single-component catalysts, inorder to omit a complicated catalyst synthesis process.

As catalysts of excellent polymerization activity, those using aphosphine compound or an amine compound as a Pd cation ligand and as aneutral donor and using a superstrong acid anion as a weak counter anionligand are known (see patent documents 1 and 3 to 6, non-patent document12).

Such multi-component catalysts as used in the prior art are obtained bypreparing any of the following catalyst systems.

Catalyst System I

(1) Pd compound

(2) Neutral phosphine or amine compound

(3) Ionic compound capable of becoming weak counter anion for Pd cation

(4) Organoaluminum compound

Catalyst System II

(1) Pd compound having neutral phosphine or amine compound as ligand

(2) Ionic compound capable of becoming weak counter anion for Pd cation

(3) Organoaluminum compound

Catalyst System III

(1) Pd compound having, as ligand, neutral donor having Pd—C bond, suchas σ-alkyl, σ-aryl or π-allyl

(2) Ionic compound capable of becoming weak counter anion for Pd cation

Catalyst System IV

(1) Pd compound having, as ligand, neutral donor having Pd—C bond, suchas σ-alkyl, σ-aryl or π-allyl

(2) Lewis acid compound

In any of the above catalysts, a phosphine or amine compound as aneutral donor is contained. In case of Pd compounds having, as a ligand,a neutral donor and having Pd—C bond, such as σ-alkyl, σ-aryl orπ-allyl, however, syntheses of their complexes become complicated, sothat it cannot be necessarily said that they are industriallyadvantageous. In the prior art, any catalyst having as its constituentan ionic phosphonium salt instead of such a neutral donor has not beenknown heretofore.

In the case where polymerization of5-trialkoxysilylbicyclo[2.2.1]hept-2-ene having a hydrolyzable silylgroup and bicylo[2.2.1]hept-2-ene (norbornene) having no substituent inthe side chain is carried out in a hydrocarbon solvent using aconventional neutral donor catalyst system, a polymer having acompositional distribution is liable to be produced, or precipitationsometimes take place during the polymerization, or the resulting polymersometimes becomes opaque. It is thought that this is caused by thatreactivity of the 5-trialkoxysilylbicyclo[2.2.1]hept-2-ene is higherthan that of the bicylo[2.2.1]hept-2-ene, so that the5-trialkoxysilylbicyclo[2.2.1]hept-2-ene is polymerized in a largerratio compared to a ratio of these charged monomers at the stage of thebeginning of the polymerization, and as a result, a polymer havingstructural units derived from the5-trialkoxysilylbicyclo[2.2.1]hept-2-ene in a higher proportion isformed, that is, a compositional distribution regarding the structuralunits of the polymer occurs, and consequently, solubility in thepolymerization solvent or compatibility with the polymer formed in thelatter half of the polymerization reaction is lowered.

Moreover, if a compositional distribution regarding the structural unitsderived from the 5-trialkoxysilylbicyclo[2.2.1]hept-2-ene occurs,crosslink network of a crosslinked product obtained by crosslinking thepolymer utilizing the hydrolyzable siyl group becomes ununiform, and thecrosslinked product sometimes has poor dimensional stability.

Therefore, as a polymerization process substantially bringing about nocompositional distribution, a process wherein one of the monomers iscontinuously or successively added to the polymerization system can beconsidered. However, it is thought that such a control becomes difficultif a reactivity ratio of the monomer copolymerized greatly differs.

As a means to prevent precipitation even if such a compositionaldistribution occurs, copolymerization of the5-trialkoxysilylbicyclo[2.2.1]hept-2-ene and a cycloolefin compoundhaving an alkyl group of 3 or more carbon atoms as a side chainsubstituent can be considered. In this case, however, when a film or asheet is formed from the resulting copolymer, the film or the sheet hasa too large coefficient of liner expansion though it has flexibility,and a problem of dimensional stability sometimes takes place. In thiscase, further, the compositional distribution sometimes becomes muchlarger, and therefore, a problem of transparency of the resultingpolymer and a problem of uniformity of a crosslink network of acrosslinked product formed from the polymer is liable to take place.

In the polymerization reaction of a cycloolefin compound having an estergroup or an oxetane group with the bicylo[2.2.1]hept-2-ene, reactivityof the cycloolefin compound having an ester group or an oxetane group islower than that of the bicylo[2.2.1]hept-2-ene differently from the caseof using the aforesaid cycloolefin compound having a hydrolyzable silylgroup, so that a polymer having structural units derived from thecycloolefin compound having an ester group or an oxetane group in alower proportion is formed at the stage of the beginning of thepolymerization. With regard to occurrence of a compositionaldistribution, however, this polymerization is similar to that using thecycloolefin compound having a hydrolyzable silyl group, and the sameproblems sometimes take place.

On this account, there has been desired a catalyst system which does notsubstantially bring about the aforesaid compositional distribution inthe polymerization reaction of a cycloolefin compound having a polarsubstituent such as a hydrolyzable silyl group, an ester group or anoxetane group with a non-polar cycloolefin compound and therefore whichdoes not cause precipitation or turbidity of the resulting polymerduring the polymerization using a hydrocarbon solvent.

Further, the Pd catalyst is expensive, and remaining of a large amountof the Pd catalyst in the polymer causes coloring or a lowering oftransparency of the polymer, and accordingly, there has been desired acatalyst capable of performing polymerization in a small catalyticamount and showing high polymerization activity.

Furthermore, although the multi-component catalyst containing the Pdcompound has higher resistance to water or methanol than themulti-component catalyst containing a compound of an early transitionmetal of Ti or Zr, phosphine that is added as a neutral donor to improvepolymerization activity is liable to be oxidized and becomes phosphineoxide if oxygen is present when it is stored, and as a result, loweringof polymerization activity is sometimes brought about. Especially in thepolymerization with a small catalytic amount, the catalyst becomesdifferent even in the presence of a trace amount of oxygen, and theinfluence of oxygen is great.

On this account, a catalyst system which brings about little variabilityin the polymerization rate and the quality of the resulting polymer evenin the presence of a trace amount of oxygen in the polymerization systemhas been desired from the viewpoint of industrials production.

Moreover, production of a cycloolefin addition polymer crosslinkedproduct having adhesion properties or solvent resistance and chemicalresistance usually includes a step of producing a copolymer that is aprecursor of the crosslinked product by performing additionpolymerization reaction of a cycloolefin compound having a polarsubstituent that becomes a crosslinking group, such as a hydrolyzablesilyl group or an ester group, with a non-polar cycloolefin compound.From the copolymer formed by such an addition polymerization reaction,however, removal of palladium atom is difficult in many cases, and alarge amount of residual palladium in the resulting copolymer causes aproblem of lowering of optical transparency.

Patent document 1: U.S. Pat. No. 6,455,650

Patent document 2: U.S. Pat. No. 3,330,815

Patent document 3: Japanese Patent Laid-Open Publication No. 262821/1993

Patent document 4: WO 00/20472

Patent document 5: Japanese Patent Laid-Open Publication No. 130323/1998

Patent document 6: Japanese Patent Laid-Open Publication No. 98035/2001

Non-patent document 1: Christoph Janiak, Paul G. Lassahn, Macromol.Rapid Commun. 22,. p. 479 (2001)

Non-patent document 2: R. G. Schultz, Polym. Lett. Vol. 4, p. 541 (1966)

Non-patent document 3: Stefan Breunig, Wilhelm Risse, Makromol. Chem.193, 2915 (1992)

Non-patent document 4: Adam L. Safir, Bruce M. Novak Macromolecules, 28,5396 (1995)

Non-patent document 5: Joice P. Mathew et al., Macromolecules, 29,2755-2763 (1996)

Non-patent document 6: Annette Reinmuth et al., Macromol. Rapid Commun.17 173-180 (1996)

Non-patent document 7: B. S. Heinz, Acta Polymer 48, 385 (1997)

Non-patent document 8: B. S. Heinz et al., Macromol. Rapid Commun. 19,251 (1998)

Non-patent document 9: Nicole R. Grove et al., J. Polym. Sci. Part B,37, 3003 (1999)

Non-patent document 10: April D. Hennis et al., organometallics, 20,2802 (2001)

Non-patent document 11: Seung UK Son et al., J. Polym. Sci. Part A,Polym. Chem. 41, 76 (2003)

Non-patent document 12: John Lipian et al., Macromolecules, 35,8969-8977 (2002)

The present invention has been made under such circumstances asdescribed above, and it is an object of the present invention to providea process for producing a cycloolefin addition polymer in which one ormore cycloolefin monomers can be addition-(co)polymerized with a smallamount of a palladium catalyst and a cycloolefin (co)polymer can beproduced with high activity.

It is another object of the present invention to provide a process forproducing a cycloolefin addition polymer using a catalyst of highpolymerization activity, in which when a monomer composition comprisinga specific cycloolefin compound and a cycloolefin compound having apolar substituent such as a hydrolyzable silyl group is polymerized, acompositional distribution regarding structural units derived from thecycloolefin compound having a polar substituent is not substantiallybrought about.

It is a further object of the present invention to provide a process forproducing a cycloolefin addition polymer using a novel catalyst whosepolymerization activity is little influenced even when a trace amount ofoxygen is present in the (co)polymerization reaction of cycloolefincompounds and which is capable of carrying out addition(co)polymerization with high activity even when monomers containing acycloolefin compound having a polar substituent such as a hydrolyzablesilyl group are (co) polymerized.

DISCLOSURE OF THE INVENTION

The process for producing a cycloolefin addition polymer of the presentinvention comprises addition-polymerizing one or more cycloolefinmonomers comprising a cycloolefin compound represented by the followingformula (1) in the presence of a multi-component catalyst comprising:

(a) a palladium compound, and

(b) one or more phosphorus compounds selected from the group consistingof the following compounds (b-1) and (b-2):

(b-1) a phosphonium salt represented by the following formula (b1):[PR²R³R⁴R⁵]⁺[CA₁]⁻   (b1)wherein P is a phosphorus atom, R² is a substituent selected from ahydrogen atom, an alkyl group of 1 to 20 carbon atoms, a cycloalkylgroup and an aryl group, R³ to R⁵ are each independently a substituentselected from an alkyl group of 1 to 20 carbon atoms, a cycloalkyl groupand an aryl group, and [CA₁]⁻ is a counter anion selected from acarboxylic acid anion, a sulfonic acid anion and a superstrong acidanion containing an atom selected from B, P and Sb and a F atom,

(b-2) an addition complex of a phosphine compound that contains asubstituent selected from an alkyl group of 3 to 15 carbon atoms, acycloalkyl group and an aryl group and has a cone angle (θ deg) of 170to 200 and an organoaluminum compound;

wherein A¹ to A⁴ are each independently an atom or a group selected fromthe group consisting of a hydrogen atom, a halogen atom, an alkyl groupof 1 to 15 carbon atoms, a cycloalkyl group, an aryl group, an estergroup, an oxetanyl group, an alkoxy group, a trialkylsilyl group and ahydroxyl group, and may be each bonded to a cyclic structure through abond group of 0 to 10 carbon atoms, said bond group containing at leastone group or atom selected from an alkylene group of 1 to 20 carbonatoms, an oxygen atom, a nitrogen atom and a sulfur atom, A¹ and A² mayform an alkylidene group of 1 to 5 carbon atoms, a substituted orunsubstituted alicyclic or aromatic ring of 5 to 20 carbon atoms or aheterocyclic ring of 2 to 20 carbon atoms, A¹ and A³ may form asubstituted or unsubstituted alicyclic or aromatic ring of 5 to 20carbon atoms or a heterocyclic ring of 2 to 20 carbon atoms, and m is 0or 1.

In the process for producing a cycloolefin addition polymer of theinvention, there are the following two preferred embodiments.

1. An embodiment wherein the multi-component catalyst comprises (a) apalladium compound, (b-1) a phosphorus compound represented by theformula (b1), and (c) a compound selected from an ionic boron compound,an ionic aluminum compound, an aluminum compound of Lewis acidity and aboron compound of Lewis acidity.

2. An embodiment wherein the multi-component catalyst comprises (a) apalladium compound, (b-2) a phosphorus compound represented by theformula (b2), and (d) an organoaluminum compound.

In the embodiment (2), the content of the organoaluminum compound (d) ispreferably in the range of 0.1 to 200 mol based on 1 gram atom ofpalladium of the palladium compound (a).

In the process for producing a cycloolefin addition polymer of theinvention, the palladium compound (a) is preferably an organiccarboxylate of palladium or a β-diketone compound of palladium.

In the process for producing a cycloolefin addition polymer of theinvention, the multi-component catalyst is preferably a catalystprepared in the presence of at least one compound selected from thegroup consisting of a polycyclic monoolefin or non-conjugated dienehaving a bicyclo[2.2.1]hept-2-ene structure, a monocyclic non-conjugateddiene and a straight-chain non-conjugated diene.

In the process for producing a cycloolefin addition polymer of theinvention, the multi-component catalyst is preferably a catalystprepared in the presence of bicyclo[2.2.1]hept-2-ene and/or abicyclo[2.2.1]hept-2-ene derivative having one or more hydrocarbongroups of 1 to 15 carbon atoms.

In the process for producing a cycloolefin addition polymer of theinvention, the cycloolefin monomers preferably contain a cycloolefincompound represented by the following formula (2)-1 or (2)-2:

wherein R¹ and R² are each a substituent selected from an alkyl group of1 to 10 carbon atoms, a cycloalkyl group and an aryl group, X is analkoxy group of 1 to 5 carbon atoms or a halogen atom, Y is a residue ofa hydroxyl group of an aliphatic diol of 2 to 4 carbon atoms, k is aninteger of 0 to 2, and n is 0 or 1.

In the process for producing a cycloolefin addition polymer of theinvention, the cycloolefin compound represented by the formula (2)-1and/or the cycloolefin compound represented by the formula (2)-2 ispreferably used in a total amount of 0.1 to 30% by mol in the wholeamount of all the cycloolefin monomers.

In the process for producing a cycloolefin addition polymer of theinvention, the cycloolefin monomer of the formula (1) wherein A¹ to A⁴are each independently a hydrogen atom or a hydrocarbon group of 1 to 15carbon atoms is preferably used in an amount of not less than 50% by molin the whole amount of all the cycloolefin monomers.

The present application declares the right of priority from JapanesePatent Application No. 296507/2003 and Japanese Patent Application No.23576/2004 and claims them by citing them.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described in detail hereinafter.

In the process for producing a cycloolefin addition polymer of theinvention, addition polymerization of one or more cycloolefin monomersis carried out using a multi-component catalyst comprising a palladiumcompound (a) and a specific phosphorus compound (b).

Multi-Component Catalyst

The multi-component catalyst for use in the invention comprises:

(a) a palladium compound, and

(b) one or more phosphorus compounds selected from the group consistingof the following compounds (b-1) and (b-2):

(b-1) a phosphonium salt represented by the following formula (b1):[PR²R³R⁴R⁵]⁺[CA₁]⁻   (b1)wherein P is a phosphorus atom, R² is a substituent selected from ahydrogen atom, an alkyl group of 1 to 20 carbon atoms, a cycloalkylgroup and an aryl group, R³ to R⁵ are each independently a substituentselected from an alkyl group of 1 to 20 carbon atoms, a cycloalkyl groupand an aryl group, and [CA₁]⁻ is a counter anion selected from acarboxylic acid anion, a sulfonic acid anion and a superstrong acidanion containing an atom selected from B, P and Sb and a F atom,

(b-2) an addition complex of a phosphine compound that contains asubstituent selected from an alkyl group of 3 to 15 carbon atoms, acycloalkyl group and an aryl group and has a cone angle (θ deg) of 170to 200 and an organoaluminum compound.

Such a multi-component catalyst for use in the invention furthercomprises, if necessary,

(c) a compound selected from an ionic boron compound, an ionic aluminumcompound, an aluminum compound of Lewis acidity and a boron compound ofLewis acidity,

and/or

(d) an organoaluminum compound.

Next, each component of the multi-component catalyst for use in theinvention is described.

(a) Palladium Compound

The palladium compound (a) is, for example, an organic carboxylate, anorganic phosphite, an organic phosphate, an organic sulfonate, aβ-diketone compound or a halide of palladium. Of these, an organiccarboxylate of palladium or a β-diketone compound of palladium ispreferable because such a compound is easily dissolved in a hydrocarbonsolvent and has high polymerization activity.

Examples of the above compounds include organic carboxylates ofpalladium, such as acetate, propionate, maleate, fumarate, butyrate,adipate, 2-ethylhexanoate, naphthenate, oleate, dodecanoate,neodecanoate, 1,2-cyclohexanedicarboxylate,bicyclo[2.2.1]hept-5-ene-2-carboxylate, 5-norbornene-2-caroxylate,benzoate, phthlate, terephthalate and naphthoate of palladium; complexesof organic carboxylates of palladium, such as triphenylphosphine complexof palladium acetate, tri(m-tolyl)phosphine complex of palladium acetateand tricyclohexylphosphine complex of palladium acetate; phosphites andphosphates of palladium, such as dibutylphosphite, dibutylphosphate,dioctylphosphate and dibutylphosphate ester salt of palladium; organicsulfonates of palladium, such as dodecylbenzenesulfonate andp-toluenesulfonate of palladium; β-diketone compounds of palladium, suchas bis(acetylacetonato)palladium,bis(hexafluoroacetylacetonato)palladium, bis(ethylacetoacetate)palladiumand bis(phenylacetoacetate)palladium; and halide complexes of palladium,such as dichlorobis(triphenylphosphine)palladium,dichlorobis[tri(m-tolylphosphine)lpalladium,dibromobis[tri(m-tolylphosphine)]palladium,dichlorobis[tri(m-xylylphosphine)]palladium,dibromobis[tri(m-xylylphosphine)]palladium, imidazole complexrepresented by [C₃H₅N₂]₂[PdCl₄] and acetonyl triphenylphosphoniumcomplex represented by [Ph₃PCH₂C(O)CH₃]₂[Pd₂Cl₆]. Also employable are0-valent palladium compounds which are combined with halides, such asaryl chloride, benzyl chloride, bromobenzene, chlorobenzene andbromonaphthalene, to form aryl or allyl palladium halides in thepresence of a specific phosphine compound described in the additioncomplex (b-2) in the invention, specifically, dibenzylidene acetonepalladium [Pd₂(dba)]₃ and tetrakis[triphenylphosphine]palladium[Pd(P(Ph)₃)₄].

In the present invention, it is also preferable to use, as the palladiumcompound (a), a compound represented by the following formula (al):Pd(R)(X)   (a1)wherein R is an anion selected from organic carboxylic acid of 1 to 20carbon atoms, organic sulfonic acid, organic phosphoric acid, mono ordiphosphoric acid ester, organic phosphorous acid and β-diketone, and Xis a halogen atom.

Although examples of the compounds represented by the formula (al) arenot specifically restricted, they include II-valent palladium halidecompounds, such as acetic acid palladium chloride, 2-ethylhexanoic acidpalladium chloride, naphthenic acid palladium chloride, oleic acidpalladium chloride, dodecanoic acid palladium chloride, neodecanoic acidpalladium chloride, dibutylphosphorous acid palladium chloride,dibutylphosphoric acid palladium chloride, palladium chloride ofphosphoric acid dibutyl ester, dodecylbenzenesulfonic acid palladiumchloride, p-toluenesulfonic acid palladium chloride andacetylacetonatopalladium chloride.

(b) Phosphorus Compound

The phosphorus compound (b) is, for example, one or more phosphoruscompounds selected from the group consisting of the following compounds(b-1) and (b-2).

(b-1) A phosphonium salt represented by the following formula (b1):[PR²R³R⁴R⁵]⁺[CA₁]⁻   (b1)wherein P is a phosphorus atom, R² is a substituent selected from ahydrogen atom, an alkyl group of 1 to 20 carbon atoms, a cycloalkylgroup and an aryl group, R³ to R⁵ are each independently a substituentselected from an alkyl group of 1 to 20 carbon atoms, a cycloalkyl groupand an aryl group, and [CA₁]⁻ is a counter anion selected from acarboxylic acid anion, a sulfonic acid anion and a superstrong acidanion containing an atom selected from B, P and Sb and a F atom.

(b-2) An addition complex of a phosphine compound that contains asubstituent selected from an alkyl group of 3 to 15 carbon atoms, acycloalkyl group and an aryl group and has a cone angle (θ deg) of 170to 200 and an organoaluminum compound.

The above phosphorus compounds are described below.

The compound (b-1) is a phosphonium salt represented by the aboveformula (b1). Although examples of the phosphonium salts for use in theinvention are not specifically restricted, they includetetraphenylphosphonium tetra(pentafluorophenyl)borate,tricyclohexylphosphonium tetra(pentafluorophenyl)borate,tricyclohexylphosphonium tetrafluoroborate, tricyclohexylphosphoniumoctanoate, tricyclohexylphosphonium acetate, tricyclohexylphosphoniumtrifluoromethanesulfonate, tricyclohexylphosphonium p-toluenesulfonate,tricyclohexylphosphonium hexafluoroacetylacetonate,tricyclohexylphosphonium hexafluoroantimonate, tricyclohexylphosphoniumdodecylbenzenesulfonate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumhexafluorophosphonate, tris(3-methylpheny)phosphoniumtetrakis(3,5-trifluoromethylphenyl)borate, trioctylphosphonium tetrakis(3,5-trifluoromethylphenyl) borate, trioctylphosphoniump-toluenesulfonate, tri(o-tolyl) phosphoniumtetra(pentafluorophenyl)borate, tri(pentafluorophenyl)phosphoniumtrifluoromethanesulfonate and tri(t-butyl)phosphoniumtrifluoromethanesulfonate. Preferable are tricylohexylphosphonium salt,tri(pentafluorophenyl)phosphonium salt and tri(o-tolyl)phosphonium salt.

In the present invention, by the use of the phosphonium salt (b-1) asthe phosphorus compound (b), a copolymer of small compositionaldistribution can be obtained by copolymerization reaction, andtherefore, it can be favorably prevented that the resulting cycloolefinaddition polymer is made to have an extremely high molecular weight togive a polymer solution in a solid and swollen state or to causeprecipitation of the polymer. On this account, the resulting cycloolefinaddition polymer can be favorably used for forming a film, a sheet, athin film or the like by a solution casting method.

The compound (b-2) is an addition complex of a phosphine compound thatcontains a substituent selected from an alkyl group of 3 to 15 carbonatoms, a cycloalkyl group and an aryl group and has a cone angle (θ deg)of 170 to 200 and an organoaluminum compound. In the present invention,it is an important technical requirement to use the specific phosphinecompound as a raw material of the component (b-2). If another phosphinecompound is used, the resulting cycloolefin addition polymer is made tohave an extremely high molecular weight to give a polymer solution in asolid and swollen state or to cause precipitation of the polymer, and inthis case, formation of a film, a sheet or a thin film by a solutioncasting method sometimes becomes difficult.

The phosphine compound used as a raw material of the component (b-2) isa trivalent electron donative phosphorus compound (tertiary phosphinecompound) having an alkyl group, a cyloalkyl group or an aryl group as asubstituent. The cone angle (θ deg) of the tertiary phosphine compoundis calculated by C. A. Tolman (Chem. Rev. Vol 77, 313 (1977)) and is aconical angle θ measured about a model that is formed by a metal atomand three substituents of a phosphorus atom and by setting a bonddistance between the metal atom and the phosphorus atom to 2.28 Å.

Preferred examples of the phosphine compounds having a cone angle (θdeg) of 170 to 200 for use in the invention includetricyclohexylphosphine, di-t-butylphenylphosphine,trineopentylphosphine, tri(t-butyl)phosphine,tri(pentafluorophenyl)phosphine and tri(o-tolyl)phosphine. Alsoavailable are di-t-butyl-2-biphenylphosphine,di-t-butyl-2′-dimethylamino-2-biphenylphosphine,dicyclohexyl-2-biphenylphosphine,dicyclohexyl-2′-i-propyl-2-biphenylphosphine, etc.

The organoaluminum compound used as a raw material of the component(b-2) acts as Lewis acid, is a compound that forms an addition complextogether with the above-mentioned phosphine compound, and is a compoundhaving at least one aluminum-alkyl bond. Such an organoaluminum compoundis preferably an organoaluminum compound having such a degree of aciditythat when the organoaluminum compound is coordinated to xanthone in amanner described in the literature “Saegusa et al., Catalysts, Vol. 7,p.43 (1965)”, a shift value (Δν_(C═O)) of an absorption spectrum ofstretching vibration given by carbonyl (C═O) of the xanthone, asmeasured by means of an infrared spectrum, is not less than 50 cm⁻¹.

Preferred examples of such organoaluminum compounds includemethylaluminum dichloride, ethylaluminum dichloride, butylaluminumdichloride, sesquiethylaluminum chloride, diethylaluminum chloride,diethylaluminum fluoride, diethylaluminum bromide, dibutylaluminumchloride, triethylaluminum, trimethylaluminum, tributylaluminum,trihexylaluminum and dibutylaluminum hydride. From the viewpoint ofdegree of acidity, alkylaluminum alkoxide compounds, such asdiethyaluminum ethoxide, diethylauminum methoxide and ethylaluminumdiethoxide, are undesirable.

The addition complex (b-2) of the specific phosphine compound and theorganoaluminum compound is usually a complex wherein a ratio between thephosphine compound and the organoaluminum compound is 1:1 by mol. Suchan addition complex can be formed by adding the organoaluminum compoundto the specific phosphine compound in an amount of 1 to 10 mol based on1 mol of the specific phosphine compound at a temperature of 0 to 100°C. and reacting them. For the formation of the complex, 1.0 mol of theorganoaluminum compound based on 1 mol of the specific phosphinecompound is enough, and excess organoaluminum compound acts as thelater-described organoaluminum (d) that is a cocatalyst component.

In the present invention, it is preferable to use the addition complex(b-2) as the phosphorus compound (b) because oxidation resistance of thecatalyst to oxygen is more increased as compared with a case of using aphosphine compound that is not in the form of a complex, and theresulting catalyst becomes stable even if it is stored in a solutionstate for a long period of time. Further, it is preferable to use theaddition complex (b-2) because even if oxygen is present in thepolymerization system, the degree of lowering of polymerization activityis low.

(c) Compound Selected from Ionic Boron Compound, Ionic AluminumCompound, Aluminum Compound of Lewis Acidity and Boron Compound of LewisAcidity

When the phosphorus compound (b-1) is used as the component (b), themulti-component catalyst for use in the invention preferably contains(c) a compound selected from an ionic boron compound, an ionic aluminumcompound, an aluminum compound of Lewis acidity and a boron compound ofLewis acidity.

Examples of the ionic boron compounds include triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyllborate, triphenylcarbeniumtetrakis(2,4,6-trifluorophenyl)borate, triphenylcarbeniumtetraphenylborate, tributylammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,N,N-diphenylanilinium tetrakis(pentafluorophenyl)borate and lithiumtetrakis(pentafluorophenyl)borate.

Examples of the ionic aluminum compounds include triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]aluminate, triphenylcarbeniumtetrakis(2,4,6-trifluorophenyl)aluminate and triphenylcarbeniumtetraphenylaluminate.

Examples of the aluminum compounds of Lewis acidity include aluminumtrifluoride ether complex, ethyldifluoroaluminum,ethoxydifluoroaluminum, tris(pentafluorophenyl)aluminum,tris(3,5-difluorophenyl)aluminum andtris(3,5-ditrifluoromethylphenyl)aluminum.

Examples of the boron compound of Lewis acidity includetris(pentafluorophenyl)boron, tris(3,5-difluorophenyl)boron,tris(3,5-ditrifluoromethylphenyl)boron and boron trifluoride ethercomplex.

Of the above compounds (c), the ionic boron compound is most preferablyused in the invention from the viewpoint of polymerization activity.

(d) Organoaluminum Compound

When the phosphorus compound (b-2) is used as the component (b), themulti-component catalyst for use in the invention preferably contains(d) an organoaluminum compound as a cocatalyst.

The organoaluminum compound (d) is an aluminum compound having at leastone aluminum-alkyl group, and examples of such compounds preferably usedinclude alkylalumoxane compounds, such as methylalumoxane,ethylalumoxane and butylalmoxane; trialkylaluminum compounds, such astrimethylaluminum, triethylaluminum and triisobutylaluminum;alkylaluminum compounds and alkylaluminum halide compounds, such asdiisobutylaluminum hydride, diethylaluminum chloride, diethylaluminumfluoride, ethylaluminum sesquichloride and ethylaluminum dichloride; andmixtures of the above alkylalumoxane compounds and the abovealkylaluminum compounds.

Preparation of Multi-Component Catalyst

The multi-component catalyst for use in the invention contains thecomponent (a), the component (b), and optionally the component (c)and/or the component (d) In the present invention, the amounts of thesecatalyst components are not specifically restricted, but thesecomponents are preferably used in the following amounts.

The palladium compound (a) is used in an amount of 0.0005 to 0.05 mmolin terms of Pd atom, preferably 0.001 to 0.05 mmol in terms of Pd atom,more preferably 0.005 to 0.01 mmol in terms of Pd atom, based on 1 molof the cycloolefin monomers. Especially when an organic carboxylate or aβ-diketone compound of palladium is used as the palladium compound, itcan be addition-polymerized in an amount of not more than 0.01 mg,preferably 0.001 to 0.01 mmol, in terms of Pd atom, based on 1 mol ofthe cyclolefin monomers.

The specific phosphorus compound (b) is used in an amount of usually0.05 to 20 mol based on 1 gram atom of Pd of the palladium compound (a).When the phosphonium salt (b-1) is used as the component (b), thephosphonium salt (b-1) is used in an amount of usually 0.5 to 20 mol,preferably 0.5 to 5 mol, based on 1 gram atom of Pd of the palladiumcompound (a). When the addition complex (b-2) is used as the component(b), the addition complex (b-2) is used in an amount of usually 0.1 to10 mol, preferably 0.5 to 3.0 mol, based on 1 gram atom of Pd of thepalladium compound (a).

The component (c) such as an ionic boron compound is particularlypreferably used when the phosphonium salt (b-1) is used as the component(b), but when the addition complex (b-2) is used as the component (b),the component (c) is used when needed. When the multi-component catalystcontains the component (c), the component (c) is used in an amount of0.2 to 20 mol, preferably 0.5 to 10 mol, more preferably 0.5 to 5 mol.based on 1 gram atom of Pd of the palladium compound (a).

The organoluaminum compound (d) is particularly preferably used when theaddition complex (b-2) is used as the component (b), but when thephosphonium salt (b-1) is used as the component (b), the organoaluminumcompound (d) is used when needed. By the use of the organoaluminumcompound, effects that the polymerization activity is improved and theresistance of the catalyst system to impurities such as oxygen isincreased can be expected. When the multi-component catalyst containsthe organoaluminum compound (d), the organoaluminum compound (d) is usedin an amount of 0.1 to 200 mol, preferably 0.5 to 200 mol, based on 1gram atom of Pd of the palladium compound (a). When the phosphonium salt(b-1) is used as the component (b), the organoaluminum compound (d) isused in an amount of 0.5 to 10 mol based on 1 gram atom of Pd of thepalladium compound (a), and when the addition complex (b-2) is used asthe component (b), the organoaluminum compound (d) is used in an amountof 0.5 to 20 mol based on 1 gram atom of Pd of the palladium compound(a).

In the present invention, the multi-component catalyst comprising theabove-mentioned components has only to be present in the polymerizationsystem, and the preparation process such as order of addition of thecatalyst components or the use method is not specifically restricted.That is to say, the components to constitute the multi-componentcatalyst may be previously mixed and the mixture is then added to thecycloolefin monomers, or they may be simultaneously or successivelyadded directly to the polymerization system where the cycloolefinmonomers are present.

Although the multi-component catalyst for use in the invention may beprepared by simply mixing the catalyst components or by adding them tothe polymerization system as described above, it is also preferable toprepare the multi-component catalyst in the presence of a compoundselected from a polycyclic monoolefin compound having abicyclo[2.2.1]hept-2-ene structure, a polycyclic non-conjugated dienehaving a bicyclo[2.2.1]hept-2-ene structure, and a monocyclic orstraight-chain conjugated diene or non-conjugated diene (said compoundbeing also referred to as a “compound such as diene” hereinafter)Especially when the addition complex (b-2) is used as the component (b),preparation of the catalyst is desirably carried out in the presence ofthe compound such as diene. When the compound such as diene is used inthe preparation of the multi-component catalyst, the compound such asdiene can be used in an amount of usually 0.5 to 1000 mol based on 1gram atom of Pd of the palladium compound (a). If the preparation of themulti-component catalyst is carried out in the presence of astraight-chain monoolefin compound and/or a monocyclic monoolefincompound, the polymerization activity of the catalyst is sometimesinsufficient. If the preparation of the multi-component catalyst iscarried out in the presence of a straight-chain conjugated ornon-conjugated triene or higher polyene, the catalyst sometimes becomessolvent-insoluble or gelation of the resulting polymer sometimes takesplace.

In the case where a polycyclic monoolefin having abicyclo[2.2.1]hept-2-ene structure is used as a monomer andpolymerization is carried out by introducing the catalyst componentsinto the polymerization system in which the above monomer is present, noother compound such as diene than the polymerization monomer may be usedin the preparation of the multi-component catalyst.

Examples of the polycyclic monoolefin compounds havingbicyclo[2.2.1]hept-2-ene structure employable in the preparation of themulti-component catalyst include:

bicyclo[2.2.1]hept-2-ene,

tricyclo[5.2.1.0^(2,6)]dec-8-ene,

tricyclo[6.2.1.0^(2,7)]undec-9-ene,

tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene, and

compounds wherein the above compounds are substituted with alkyl of 1 to15 carbon atoms, cycloalkyl or aryl,

each of said compounds being employable also as the later-describedspecific monomer (1).

Examples of the polycyclic non-conjugated diene compounds havingbicyclo[2.2.1]hept-2-ene structure include:

bicyclo[2.2.1]hepta-2,5-diene,

tricyclo[5.2.1.0^(2,6)]deca-3,8-diene,

tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodeca-4,9-diene,

pentacyclo[9.2.0^(2,10).0^(3,8).1^(1,11).1^(4,7)]pentadeca-5,12-diene,

1,4-bis(2-bicyclo[2.2.1]hept-5-enyl)butane,

1,4-bis (2-bicyclo[2.2.1]hept-5-enyl) hexane,

1,4-bis(2-bicyclo[2.2.1]hept-5-enylmethyl)benzene,

dimethylbis(2-bicyclo[2.2.1]hept-5-enylmethyl)silane,

methyltris(2-bicyclo[2.2.1]hept-5-enylmethyl)silane,

5-vinylbicyclo[2.2.1]hept-2-ene,

5-vinylidenebicyclo[2.2.1]hept-2-ene, and

5-isopropylidenebicyclo[2.2.1]hept-2-ene.

Examples of the straight-chain conjugated diene compounds include1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene,2-phenyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene.

Examples of the monocyclic conjugated diene compounds include1,3-cyclohexadiene and 1,3-cylclooctadiene.

Examples of the straight-chain non-conjugated diene compounds include1,4-hexadiene and 1,5-hexadiene.

Examples of the monocyclic non-conjugated diene compounds include1,4-cyclohexadiene and 1,5-cyclooctadiene.

From the viewpoint of polymerization activity, it is preferable to carryout preparation of the multi-component catalyst for use in the inventionin the presence of a compound selected from the polycyclic monoolefinhaving a bicyclo[2.2.1]hept-2-ene structure, the polycyclicnon-conjugated diene having a bicyclo[2.2.1]hept-2-ene structure and themonocyclic non-conjugated diene among the above compounds.

The catalyst formed from the components (a) and (b) and optionally thecomponents (c) and (d) sometimes has low solubility in a hydrocarbonsolvent, and depending upon the type of the polymerization solvent,precipitation sometimes takes place temporarily to lower thepolymerization activity when the catalyst is added to the polymerizationsystem. However, when preparation of the multi-component catalyst foruse in the invention is carried out in the presence of the compound suchas diene, the problem of lowering of polymerization activity can belightened or eliminated. This effect is thought to be attributable tothat a complex is formed between the compound such as diene and themulti-component catalyst when the multi-component catalyst is preparedin the presence of the compound such as diene. Moreover, in the casewhere the complex formed between the compound such as diene and thecatalyst becomes a starting active site of the polymerization reaction,polymer chains extend in two directions in the polymerization, so thatit becomes possible to obtain a polymer having a wide molecular weightdistribution.

As the process for preparing the multi-component catalyst in thepresence of the compound such as diene, there can be mentioned, forexample, a) a process wherein the catalyst components (a) and (b) and ifnecessary the catalyst components (c) and (d) are previously mixed inthe presence of the compound such as diene to prepare a catalyst andthen the catalyst is added to a mixture of a monomer and apolymerization solvent, and b) a process wherein the catalyst components(a) and (b) and if necessary the catalyst components (c) and (d) aredirectly or successively added to a mixture of a monomer, apolymerization solvent and the compound such as diene to prepare acatalyst. In these processes, the order of addition of the catalystcomponents is not specifically restricted.

As the process for preparing the multi-component catalyst, further, c) aprocess wherein the addition complex (b-2) of a specific phosphinecompound and a complex-forming organoaluminum compound is formed in thepresence of a mixture of a monomer and a hydrocarbon solvent and thenthe catalyst component (a) and if necessary the catalyst components (c)and/or (d) are added is also employable. In this process, of theorganoaluminum compound used for forming the addition complex (b-2), theexcess organoaluminum compound, i.e., a portion exceeding 1 mol based on1 mol of the specific phosphine compound, acts as an organoaluminumcompound that is the optionally added component (d) functioning as acocatalyst, so that it is possible to decrease the amount of theorganoaluminum compound finally added as the component (d) or omit theorganoaluminum compound.

Cycloolefin Monomer

In the process for producing a cycloolefin addition polymer of theinvention, one or more cycloolefin monomers comprising a cycloolefincompound represented by the following formula (1) (referred to as a“specific monomer (1)” hereinafter) are addition-polymerized.

In the formula (1), A¹ to A⁴ are each independently an atom or a groupselected from the group consisting of a hydrogen atom, a halogen atom,an alkyl group of 1 to 15 carbon atoms, a cycloalkyl group, an arylgroup, an ester group, an oxetanyl group, an alkoxy group, atrialkylsilyl group and a hydroxyl group, and may be each bonded to acyclic structure through a bond group of 0 to 10 carbon atoms, said bondgroup containing at least one group or atom selected from an alkylenegroup of 1 to 20 carbon atoms, an oxygen atom, a nitrogen atom and asulfur atom, A¹ and A² may form an alkylidene group of 1 to 5 carbonatoms, a substituted or unsubstituted alicyclic or aromatic ring of 5 to20 carbon atoms or a heterocyclic ring of 2 to 20 carbon atoms, A¹ andA³ may form a substituted or unsubstituted alicyclic or aromatic ring of5 to 20 carbon atoms or a heterocyclic ring of 2 to 20 carbon atoms, andm is 0 or 1.

Examples of the specific monomers (1) are given below, but the-inventionis not limited to those examples.

Bicyclo[2.2.1]hept-2-ene,

5-Methyl-bicyclo[2.2.1]hept-2-ene,

5-Ethylbicyclo[2.2.1]hept-2-ene,

5-Propylbicyclo[2.2.1]hept-2-ene,

5-Butylbicyclo[2.2.1]hept-2-ene,

5-(1-Butenyl)bicyclo[2.2.1]hept-2-ene,

5-Pentylbicyclo[2.2.1]hept-2-ene,

5-Hexylbicyclo[2.2.1]hept-2-ene,

5-Heptylbicyclo[2.2.1]hept-2-ene,

5-Octylbicyclo[2.2.1]hept-2-ene,

5-Decylbicyclo[2.2.1]hept-2-ene,

5-Dodecylbicyclo[2.2.1]hept-2-ene,

5-Cyclohexyl-bicyclo[2.2.1]hept-2-ene,

5-Vinylbicyclo[2.2.1]hept-2-ene,

5-Allylbicyclo[2.2.1]hept-2-ene,

5-Ethylidenebicyclo[2.2.1]hept-2-ene,

5-Phenylbicyclo [2.2.1]hept-2-ene,

5,6-Dimethylbicyclo[2.2.1]hept-2-ene,

5-Methyl-6-ethylbicyclo[2.2.1]hept-2-ene,

5-Fluoro-bicyclo[2.2.1]hept-2-ene,

5-Chloro-bicyclo[2.2.1]hept-2-ene,

5-Benzyl-bicyclo[2.2.1]hept-2-ene,

5-Indanyl-bicyclo[2.2.1]hept-2-ene,

5-Trimethylsilyl-bicyclo[2.2.1]hept-2-ene,

5-Triethylsilyl-bicyclo[2.2.1]hept-2-ene,5-Methoxy-bicyclo[2.2.1]hept-2-ene,

5-Ethoxy-bicyclo[2.2.1]hept-2-ene,

Tricyclo[5.2.1.0^(2,6)]dec-8-ene,

Tricyclo[5.2.1.0^(2,6)]deca-3,8-diene,

Tricyclo[6.2.1.0^(2,7)]undec-9-ene,

Tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Methyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Ethyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

Methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate,

t-Butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate,

Methyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate,

Bicyclo[2.2.1]hept-5-ene-2,3-carboxylic anhydride,

Bicyclo[2.2.1]hept-5-ene-N-cyclohexyl-2,3-carbonimide,

Bicyclo[2.2.1]hept-5-ene-N-phenyl-2,3-carbonimide,

Bicyclo[2.2.1]hept-5-ene-2-spiro-3′-exo-succinic anhydride,

Methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate-methyl 2-carboxylate,

Bicyclo[2.2.1]hept-5-ene-2-spiro-butyrolactone,

Bicyclo[2.2.1]hept-5-ene-2-spiro-N-cyclohexyl-succinimide,

Bicyclo[2.2.1]hept-5-ene-2-spiro-N-phenyl-succinimide,

Methyl tetracyclo[6.2.1.1^(3,6).0^(2,7)Idodec-9-ene-4-carboxylate,

Methyl4-methyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-9-ene-4-carboxylate,

5-[(3-Ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]hept-2-ene,

5-[(3-Oxetanyl)methoxy]bicyclo[2.2.1]hept-2-ene,

Spiro-5-(3-oxetanyl)bicyclo[2.2.1]hept-2-ene, and

(3-Eethyl-3-oxetanyl)methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate.

The above specific monomers (1) may be used singly or in combination oftwo or more kinds.

In the present invention, it is also preferable to use, as a cycloolefinmonomer, the specific monomer (1) of the formula (1) wherein A¹ to A⁴are each independently a hydrogen atom or a hydrocarbon group of 1 to 15carbon atoms, in an amount of not less than 50% by mol in the wholeamount of all the cycloolefin monomers.

In the present invention, the cycloolefin monomers also preferablyfurther contain, in addition to the specific monomer (1), a cycloolefincompound represented by the following formula (2)-1 and/or a cycloolefincompound represented by the following formula (2)-2 (referred to as a“specific monomer (2)” hereinafter) When the cycloolefin monomerscontaining the specific monomer (2) are used, crosslinkability can beimparted to the resulting cycloolefin addition polymer. That is to say,by the use of the cycloolefin monomers containing the specific monomer(2), a hydrolyzable silyl group can be introduced into the molecule ofthe cycloolefin addition polymer, and the hydrolyzable silyl group actsas a crosslink site due to a siloxane bond. Further, the hydrolyzablesilyl group also acts as a site for adhesion to other members, andtherefore, it can be expected that use of the cycloolefin monomerscontaining the specific monomer (2) contributes to improvement ofadhesion of the cycloolefin addition polymer to other members.

In the formulas (2)-1 and (2)-2, R¹ and R² are each a substituentselected from an alkyl group of 1 to 10 carbon atoms, a cycloalkyl groupand an aryl group,

X is an alkoxy group of 1 to 5 carbon atoms or a halogen atom,

Y is a residue of a hydroxyl group of an aliphatic diol of 2 to 4 carbonatoms,

k is an integer of 0 to 2, and

n is 0 or 1.

Examples of the specific monomers (2) represented by the formula (2)-1or the formula (2)-2 are given below, but the invention is not limitedto those examples.

Examples of the specific monomers (2) represented by the formula (2)-iinclude the following compounds.

5-Trimethoxysilyl-bicyclo[2.2.1]hept-2-ene,

5-Triethoxysilyl-bicyclo[2.2.1]hept-2-ene,

5-Methyldimethoxysilyl-bicyclo[2.2.1]hept-2-ene,

5-Methyldiethoxysilyl-bicyclo[2.2.1]hept-2-ene,

5-Methyldichlorosilyl-bicyclo[2.2.1]hept-2-ene,

9-Trimethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Triethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Methyldimethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Ethyldimethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Cyclohexyldimethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Phenyldimethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Dimethylmethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Trichlorosilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Dichloromethylsilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

-   9-Chlorodimethylsilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Chlorodimethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Dichloromethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene, and

9-Chloromethylmethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene.

The above compounds may be used singly or in combination of two or morekinds.

Examples of the specific monomers (2) represented by the formula (2)-2include the following compounds.

5-[1′-Methyl-2′,5′-dioxa-1′-silacyclopentyl]-bicyclo[2.2.1]hept-2-ene,

5-[1′-Phenyl-2′,5′-dioxa-1′-silacyclopentyl]-bicyclo[2.2.1]hept-2-ene,

9-[1′-Methyl-2′,5′-dioxa-1′-silacyclopentyl]-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,and

9-[1′-Phenyl-2′,5′-dioxa-1′-silacyclopentyl]-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene.

The above compounds may be used singly or in combination of two or morekinds. One or more of the compounds represented by the formula (2)-1 andone or more of the compounds represented by the formula (2)-2 may beused in combination.

Of the above specific monomers (2), preferable are the followingcompounds.

5-Trimethoxysilyl-bicyclo[2.2.1]hept-2-ene,

5-Triethoxysilyl-bicyclo[2.2.1]hept-2-ene,

5-Methyldimethoxysilyl-bicyclo[2.2.1]hept-2-ene,

9-Trimethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Methyldimethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

9-Triethoxysilyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene,

5-[1′-Methyl-2′,6′-dioxa-4′,4′-dimethyl-1′-silacyclohexyl]-bicyclo[2.2.1]hept-2-ene,and

5-[1′-Methyl-2′,6′-dioxa-4′-methyl-1′-silacyclohexyl]-bicyclo[2.2.1]hept-2-ene.

In the present invention, the amounts of the specific monomer (1) andthe specific monomer (2) are not particularly restricted, and they haveonly to be properly selected according to the properties required forthe resulting polymer. However, the specific monomer (1) is usually usedin an amount of not less than 50% by mol based on the whole amount ofall the monomers, and the specific monomer (2) is usually used in anamount of 0.1 to 30% by mol based on the whole amount of all themonomers.

In the present invention, it is preferable to use the specific monomer(1) and the specific monomer (2) in combination, and in this case, theyare desirably used in such amounts that the total amount of the specificmonomer (1) and the specific monomer (2) becomes not less than 80% bymol based on the whole amount of all the monomers and that the ratio(1)/(2) becomes 70-99.8/30-0.2, preferably 80-97/20-3, more preferably85-95/15-5. By the use of these monomers (1) and (2) in such amounts,adhesion properties of the resulting polymer to other materials can beenhanced, and water (moisture) absorption distortion can besubstantially inhibited. Moreover, crosslinking utilizing a specificpolar group derived from the specific monomer (2) is facilitated, and acoefficient of linear expansion of the resulting crosslinked productbecomes extremely low.

When the cycloolefin monomers contain the specific monomer (2) in thepresent invention, the specific monomer (2) is desirably used in anamount of 0.1 to 30% by mol, preferably 2 to 30% by mol, more preferably5 to 20% by mol, in the whole amount of all the cycloolefin monomers.

In the case where the cycloolefin monomers containing the specificmonomer (2) in the above amount are used, a cycloolefin additioncopolymer containing a hydrolyzable silyl group is obtained, and whenthe resulting addition copolymer is processed into a crosslinked film,the film has excellent solvent resistance, excellent chemicalresistance, small heat shrinkage and adhesion properties, so that theabove amount is preferable. If the amount of the specific monomer (2)exceeds 30% by mol in the whole amount of all the cycloolefin monomers,lowering of polymerization activity sometimes takes place, or increaseof water absorption of the resulting addition polymer sometimes takesplace to cause water absorption distortion.

If a compound having an alkyl group of 3 to 15 carbon atoms or analkenyl group is used as the specific monomer (1), a crosslinked productobtained by crosslinking the resulting polymer or by crosslinking ahydrogenation product that is obtained by hydrogenating olefinicunsaturated bonds of the resulting polymer tends to have a largecoefficient of linear expansion, and in the uses requiring strict heatdistortion, this sometimes becomes a problem.

In the present invention, a monomer copolymerizable with the specificmonomer (1) or (2) (referred to as a “copolymerizable monomer”hereinafter) can be used in combination. Examples of the copolymerizablemonomers include cycloolefins, such as cyclopentene, cyclohexene,cycloheptene and cyclooctene; cyclodiolefins, such as cyclopentadieneand cyclohexadiene; and alky substituted derivatives thereof. Althoughthe amount of such a monomer is appropriately selected according to theproperties required for the resulting polymer, it is in the range ofusually 0 to 50% by mol, preferably 0 to 20% by mol, based on the wholeamount of all the monomers.

When the cyclodiolefin is used, it is preferable to hydrogenate olefinicunsaturated bonds remaining after polymerization in order to preventcoloring of the resulting polymer attributable to heat or light. Ahigher degree of hydrogenation is preferable, and the degree ofhydrogenation is usually not less than 90%.

In the present invention, it is preferable that the cycloolefin monomerscontain no other monomer than the specific monomer (1) and the specificmonomer (2), though it is not specifically restricted.

Production of Cycloolefin Addition Polymer Addition Polymerization

In the production process of the invention, the monomers described aboveare addition-polymerized in the presence of the multi-component catalystconsisting of the aforesaid components.

In the present invention, a specific olefin compound can be used incombination with the multi-component catalyst consisting of theaforesaid components, and by the use of the specific olefin compound incombination, enhancement of polymerization activity can be expected.Examples of such specific olefin compounds include ethylene, vinylchloride, vinyl acetate and acrylic ester. Of these, ethylene ispreferable. The specific olefin compound can be used in an amount of 1to 10,000 mol based on 1 gram atom of Pd of the palladium compound (a).

The addition polymerization in the invention is carried out usually in apolymerization solvent. Examples of the solvents employable for theaddition polymerization in the invention include alicyclic hydrocarbonsolvents, such as cyclohexane, cyclopentane and methylcyclopentane;aliphatic hydrocarbon solvents, such as hexane, heptane and octane;aromatic hydrocarbon solvents, such as toluene, benzene, xylene,ethylbenzene and mesitylene; and halogenated hydrocarbon solvents, suchas dichloromethane, 1,2-dichoroethane, 1,1-dichloroethane,tetrachloroethane, chlorobenzene and dichlorobenzene. It is preferableto use a non-halogen type solvent from the viewpoint of environmentalprotection. In the present invention, the above solvents may be usedsingly, or a mixed solvent of two or more kinds of the above solventsmay be used.

In the addition polymerization in the invention, the polymerizationtemperature is in the range of usually −20 to 120° C, preferably 20 to100° C, and the temperature can be changed with the process ofpolymerization.

In the present invention, the monomers may be added at once or may beadded successively. When two or more monomers are used, thecompositional distribution control of the resulting polymer can becarried out according to a difference in the copolymerization reactivityand a method for adding the monomers, and various copolymers of a randomcopolymer having no compositional distribution to a copolymer having acompositional distribution are obtainable. As the polymerizationprocess, any of a batch polymerization process and a continuouspolymerization process using a tank reactor, a column reactor, a tubereactor or the like is adoptable.

In the present invention, by the addition polymerization of thecycloolefin monomers comprising the specific monomer (1), a structuralunit represented by the following formula (3) is formed. The structuralunit represented by the formula (3) may be formed by furtherhydrogenating the resulting polymer after the addition polymerization,as described later.

In the formula (3), A¹ to A⁴ and m have the same meanings as those inthe formula (1).

In the case where the cycloolefin monomers contain the specific monomer(2)-1 and/or the specific monomer (2)-2, the specific monomer (1) andthe specific monomer (2) are addition-polymerized, whereby a structuralunit represented by the following formula (4)-1 or (4)-2 is formed inaddition to the structural unit represented by the formula (3).

In the formulas (4)-1 and (4)-2, R¹, R², X, Y, k and n have the samemeanings as those in the formulas (2)-1 and (2)-2.

In the present invention, termination of the addition polymerization iscarried out by adding a compound selected from organic carboxylic acidcompounds, alcohol compounds, primary to tertiary amine compounds,hydroxylamine compounds, ammonia, hydrogen, allyl halide compounds,methylaryl halide compounds, tertiary alkyl halide compounds, acylhalide compounds, silane compounds having Si—H bond, etc. to the polymersolution.

In the present invention, control of a molecular weight of thecycloolefin addition polymer is carried out by the use of olefins, suchas ethylene, propylene, 1-butene and 1-hexene, trimethylsilylethylene,trimethoxyethylene, triethoxyethylene, styrene, cyclopentene,cyclohexadiene, silane compounds, such as triethylsilane, diethylsilane,phenylsilane and diphenylsilane, isopropanol, water, hydrogen, etc., andof these, ethylene is preferable because control of the molecular weightcan be made by the use of a small amount and ethylene has no influenceon the polymerization activity.

Hydrogenation

In the case where olefinic unsaturated bonds are present in the additionpolymer obtained, e.g., a case where the specific monomer (1) havingolefinic unsaturated bonds as a side chain substituent is used, theolefinic unsaturated bonds cause coloring due to heat or light ordeterioration such as gelation, so that it is preferable to hydrogenatethe olefinic unsaturated bonds. A higher degree of hydrogenation ispreferable, and the degree of hydrogenation is desired to be usually notless than 90%, preferably not less than 95%, more preferably not lessthan 99%.

The hydrogenation method is not specifically restricted, and a usualmethod to hydrogenate olefinic unsaturated bonds can be applied. Ingeneral, hydrogenation is carried out in an inert solvent in thepresence of a hydrogenation catalyst at a hydrogen gas pressure of 0.5to 15 MPa and a reaction temperature of 0 to 200° C. When aromatic rings(aromatic groups) are present in the polymer, the aromatic rings arerelatively stable to heat or light and sometimes contribute to opticalproperties or heat resistance, so that the aromatic rings do notnecessarily have to be hydrogenated. Depending upon the desiredproperties, it is necessary to select conditions under which thearomatic rings are not substantially hydrogenated.

Examples of the inert solvents employable for the hydrogenation reactioninclude aliphatic hydrocarbons of 5 to 14 carbon atoms, such as hexane,heptane, octane and dodecane, and alicyclic hydrocarbons of 5 to 14carbon atoms, such as cyclohexane, cycloheptane, cyclodecane andmethylcyclohexane. When hydrogenation is carried out under suchconditions that the aromatic rings are not hydrogenated, aromatichydrocarbons of 6 to 14 carbon atoms, such as benzene, toluene, xyleneand ethylbenzene, are also employable.

Examples of the hydrogenation catalysts include solid catalysts in whichthe group VIII metals, such as nickel, palladium, platinum, rutheniumand rhodium, or compounds thereof are supported on porous carriers, suchas carbon, alumina, silica, silica alumina and diatomaceous earth, andhomogeneous catalysts, e.g., organic carboxylates of the group IV to thegroup VIII metals, such as cobalt, nickel and palladium, combinations ofβ-diketone compounds and organoaluminum or organolithium, and complexesof ruthenium, rhodium or iridium.

Decatalyst

In the production process of the invention, the catalyst used for thepolymerization reaction and the catalyst used for the hydrogenationreaction that is optionally performed are preferably removed in adecatalyst step. The method applied to the decatalyst step is notspecifically restricted and appropriately selected according theproperties or the shapes of the catalysts used.

In the present invention, the decatalyst operation is carried out bytreating a solution of the polymer obtained after termination of thepolymerization or a solution of a hydrogenation product of the polymerwith an aqueous solution of an oxycarboxylic acid, such as lactic acid,glycolic acid, β-methyl-β-oxypropionic acid or γ-oxybutyric acid, or anaqueous solution of triethanolamine, dialkylethanolamine,ethylenediaminetetraacetate or the like, or treating the solution withan adsorbent, such as diatomaceous earth, silica, alumina or activatedcarbon.

Further, from the solution from which the catalysts have been removed,the solvent is directly removed by evaporation, or the resulting polymeris solidified by the use of alcohols, such as methanol, ethanol andpropanol, or ketones, such as acetone and methyl ethyl ketone, and thendried, whereby the desired cycloolefin addition polymer is obtained.

Recovery

In the production process of the invention, the cycloolefin additionpolymer produced through the steps of polymerization, decatalyst, etc.can be recovered by publicly known methods, such as a method of directlyremoving a solvent from the solution containing the polymer by means ofheating, pressure reduction or the like and a method of mixing thesolution containing the polymer with a poor solvent for the polymer,such as alcohol or ketone, to solidify and separate the polymer. Thepolymer can be recovered also by using the solution as such as a rawmaterial and processing it into a film or a sheet by a solution castingmethod (casting method).

Cycloolefin Addition Polymer

The glass transition temperature (Tg) of the cycloolefin additionpolymer obtained by the production process of the invention isdetermined according to the types and the amounts of the monomers usedfor the polymerization, and has only to be properly selected accordingto the use application of the polymer. The glass transition temperatureof the polymer is in the range of usually 150 to 450° C, preferably 180to 400° C., more preferably 200 to 380° C. If the glass transitiontemperature of the polymer is lower than 150° C., a problem of heatresistance sometimes takes place. On the other hand, if the glasstransition temperature exceeds 450° C., the polymer becomes too rigid tothereby lower toughness, and as a result, the polymer is liable to bebroken.

In the present invention, the glass transition temperature of thecycloolefin addition polymer is determined as a peak temperature oftemperature dispersion of Tan5 that is measured as a dynamicviscoelasticity (storage elastic modulus: E′, loss elastic modulus: E″,Tan δ=E″/E′)

In the present invention, the molecular weight of the cycloolefinaddition polymer is measured by gel permeation chromatography at 120° C.using o-dichlorobenzene as a solvent. The cycloolefin addition polymerhas a number-average molecular weight (Mn), in terms of polystyrene, of10,000 to 300,000 and a weight-average molecular weight (Mw), in termsof polystyrene, of 30,000 to 500,000, and preferably has anumber-average molecular weight (Mn) of 30,000 to 200,000 and aweight-average molecular weight (Mw) of 50,000 to 300,000.

If the cycloolefin addition polymer has a number-average molecularweight (Mn) of less than 10,000 and a weight-average molecular weight(Mw) of less than 30,000, a film or a sheet formed from the polymer isliable to be broken. If the cycloolefin addition polymer has anumber-average molecular weight (Mn) exceeding 300,000 and aweight-average molecular weight (Mw) exceeding 500,000, the solutionviscosity of the polymer becomes too high and handling of the polymersolution sometimes becomes difficult when a film or a sheet is formed bycasting (solution casting).

To the cycloolefin addition polymer in the invention, an antioxidantselected from antioxidants of phenol type, phosphorus type, thioethertype and lactone type can be added in an amount of 0.001 to 5 parts byweight, preferably 0.01 to 5 parts by weight, based on 100 parts byweight of the polymer, whereby heat deterioration can be furtherimproved.

In order to improve processability or mechanical properties such astoughness, to the cycloolefin addition polymer in the invention can befurther added another cycloolefin addition polymer, a hydrogenatedcycloolefin ring-open polymer, an addition copolymer of α-olefin andcycloolefin, a crystalline α-olefin polymer, an α-olefin copolymer ofrubber-like ethylene and α-olefin of 3 or more carbon atoms, ahydrogenated butadiene polymer, a hydrogenated butadiene/styrene blockcopolymer, a hydrogenated isoprene polymer or the like in an amount of0.1 to 90% by weight.

The cycloolefin addition polymer in the invention may be subjected tocrosslinking. The crosslinking can be carried out by solution-castingthe polymer solution or dispersion containing an acid generator asdescribed above and then subjecting it to external heating or lightirradiation before, during or after the drying step in the aforesaidfilm- or sheet-forming process.

In the case where the cycloolefin addition polymer in the invention hasa hydrolyzable silyl group or an oxetane group in at least a part of astructural unit, a crosslinked cycloolefin addition polymer can beobtained by adding a compound (acid generator) that generates an acid bythe action of heat or light to the polymer and subjecting the polymer tolight irradiation or heating.

The cycloolefin addition polymer having the aforesaid structural unit(4)-1 or (4)-2 (referred to as a “hydrolyzable silyl group-containingpolymer” hereinafter) obtained by the production process of theinvention has a hydrolyzable silyl group as a side chain substituent,and hence, by performing hydrolysis and condensation in the presence ofan acid, a polymer crosslinked with a siloxane bond can be obtained.When the crosslinked product is processed into a film or a sheet, thefilm or the sheet has an extremely decreased coefficient of linearexpansion and also has excellent solvent resistance, chemical resistanceand liquid crystal resistance.

In the present invention, the crosslinked product can be obtained byadding a compound (acid generator) that generates an acid by the actionof heat or light to a solution of the hydrolyzable silylgroup-containing polymer, forming a film or a sheet by solution casting(casting), and subjecting the film or the sheet to light irradiation orheating to generate an acid and thereby promote crosslinking.

The acid generator for use in the invention is a compound selected fromthe following groups (1), (2), (3) and (4), and at least one compoundselected from them is desirably used in an amount of 0.0001 to 5 partsby weight, preferably 0.001 to 5 parts by weight, based on 100 parts byweight of the hydrolyzable silyl group-containing polymer.

(1) Compounds which generate Brensted acid or Lewis acid by lightirradiation, e.g., onium salts which are diazonium salts, ammoniumsalts, iodonium salts, sulfonium salts or phosphonium salts, each havingno substituent or having alkyl group, aryl group or heterocyclic groupand having, as counter anion, sulfonic acid, boron acid, phosphoricacid, antimonic acid or carboxylic acid; halogenated organic compounds,such as halogen-containing oxadiazole, a halogen-containing triazinecompound, a halogen-containing acetophenone compound and ahalogen-containing benzophenone compound; quinonediazide compounds, suchas 1,2-benzoquinonediazido-4-sulfonic acid ester,1,2-naphthoquinonediazido-4-sulfonic acid ester; and diazomethanecompounds, such as α,α′-bis(sulfonyl)diazomethane andα-carbonyl-α′-sulfonyldiazomethane.

(2) Compounds which generate an acid by heating to a temperature of notlower than 50° C., e.g., aromatic sulfonium salts, aromatic ammoniumsalts, aromatic pyridinium salts, aromatic phosphonium salts, aromaticiodonium salts, hydrazinium salts, and iron salts of metallocene, eachhaving counter anion selected from BF₄, PF₆, AsF₆, SbF₆, B(C₆F₅)₄ andthe like.

(3) Compounds which generate an acid by heating to a temperature of notlower than 50° C. in the presence or absence of water, e.g.,trialkylphosphorous acid ester, triarylphosphorous acid ester,dialkylphosphorous acid ester, monoalkylphosphorous acid ester,hypophosphorous acid ester, secondary or tertiary alcohol ester oforganic carboxylic acid, hemiacetal ester of organic carboxylic acid,trialkylsilyl ester of organic carboxylic acid, and an ester compound oforganic sulfonic acid and secondary or tertiary alcohol.

(4) Oxides of metals, such as tin, aluminum, zinc, titanium andantimony, alkoxide compounds thereof, phenoxide compounds thereof,β-diketone compounds thereof, alkyl compounds thereof, halide compoundsthereof, and organic acid salt compounds thereof.

Of these, the compounds selected from the groups (1), (2) and (3) arepreferable, and the compounds of the group (3) are particularlypreferable because they have excellent compatibility with thehydrolyzable silyl group-containing polymer and exhibit excellentstorage stability when they are added to the solution containing thehydrolyzable silyl group-containing polymer. The above acid generatorsmay be used singly, or may be used in combination of two or more kinds.

The method for forming the cycloolefin addition polymer of the inventionor a composition containing the polymer is not specifically restricted,but for example, the cycloolefin polymer or a composition containing thepolymer can be formed into a film, a sheet or a thin film by a solutioncasting method comprising dissolving or dispersing the cycloolefinpolymer or a composition containing the polymer, applying the solutionor the dispersion onto a substrate and then drying it to remove thesolvent. The solution casting method is preferable because production ofa polymer due to heat history can be inhibited.

The solution casting method for forming a film, a sheet or a thin filmis more specifically a method comprising casting a polymer solutionhaving been adjusted to a desired concentration and having beenoptionally subjected to filtration and defoaming on a release plate thatflows on a roll, passing the solution between the casting roll and asmoothing roll that is in contact with the casting roll to adjust thethickness and to smooth the surface, then evaporating the solvent,taking away the release plate and passing the film or the like through adrying machine. When there is strict requirement for the residualsolvent, it is effective to perform, in addition to the primary dryingusing a drying machine, secondary drying comprising immersion in alow-boiling halogen solvent, such as methylene chloride or1,2-dichloroethane, or exposure to an atmosphere of vapor of thelow-boiling halogen solvent, or contact with water vapor, and thenheating at a temperature of 80 to 220° C.

Crosslinking of the film, the sheet or the thin film is carried out bysolution-casting the polymer solution or dispersion containing an acidgenerator as described above and then subjecting it to external heatingor light irradiation before, during or after the drying step.

The content of the residual solvent in the film, the sheet or the thinfilm obtained by the above method is not more than 5,000 ppm, preferablynot more than 2,000 ppm, more preferably not more than 1,000 ppm. If thecontent of the residual solvent exceeds 5,000 ppm, a large amount of avolatile component is generated to cause contamination of equipments orlowering of degree of pressure reduction when a surface treatment, suchas deposition or sputtering, of the film, the sheet or the thin film iscarried out in a reduced pressure system, and moreover, the film, thesheet or the thin film has an increased coefficient of linear expansionand sometimes has poor dimensional stability.

The cycloolefin addition polymer of the invention is preferablyprocessed or formed by the solution casting as described above, but meltmolding, such as injection molding, melt extrusion molding or blowmolding, is also applicable so long as the glass transition temperatureof the polymer is not higher than 250° C. Further, even if the glasstransition temperature of the polymer exceeds 250° C., the polymer canbe formed into a sheet, a film or a thin film through melt extrusionmolding or blow molding by adding a plasticizer or allowing the polymerto swell with a solvent.

In order to further improve resistance to oxidation deterioration orresistance to coloring deterioration of the cycloolefin addition polymerof the invention, a compound selected from phenolic antioxidants,lactone antioxidants, phosphorus antioxidants and thioether antioxidantscan be added in an amount of 0.001 to 5 parts by weight based on 100parts by weight of the polymer.

In order to improve processability or mechanical properties such astoughness, to the cycloolefin addition polymer of the invention can beadded another cycloolefin addition polymer, a hydrogenated cycloolefinring-open polymer, an addition copolymer of α-olefin and cycloolefin, acrystalline α-olefin polymer, an α-olefin copolymer of rubber-likeethylene and α-olefin of 3 or more carbon atoms, a hydrogenatedbutadiene polymer, a hydrogenated butadiene/styrene block copolymer, ahydrogenated isoprene polymer or the like in an amount of 0.1 to 90% byweight.

The cycloolefin addition polymer obtained by the production process ofthe invention can be employed not only for optical material parts butalso for electronic/electric parts, medical equipment materials,electrical insulating materials and packaging materials.

Examples of the optical materials for which the cycloolefin additionpolymer is employable include light guide plates, protective films,deflection films, phase difference films, touch panels, transparentelectrode substrates, optical recording substrates, such as CD, MD andDVD, substrates for TFT, color filter substrates, optical lenses andsealing materials. Examples of the electronic/electric parts for whichthe cycloolefin addition polymer is employable include containers,trays, carrier tapes, separation films, cleaning containers, pipes andtubes. Examples of the medical equipment materials for which thecycloolefin addition polymer is employable include medicine containers,ampoules, syringes, infusion fluid bags, sample containers, test tubes,blood-collecting tubes, sterilizing containers, pipes and tubes.Examples of the electrical insulating materials for which thecycloolefin addition polymer is employable include coating materials ofelectrical wires and cables, insulating materials of OA machines such ascomputer, printer and copy machine, and insulating materials of printedboards. Examples of the packaging materials for which the cycloolefinaddition polymer is employable include packaging films for foods andmedicines.

According to the present invention, cycloolefin compounds can beaddition-(co)polymerized with high polymerization activity by the use ofa small amount of a palladium catalyst, and a cycloolefin additionpolymer can be produced with high productivity.

According to the present invention, further, especially when cycloolefinmonomers are polymerized using a multi-component catalyst comprising (a)a palladium compound, (b-1) a specific phosphonium salt and (d) anorganoaluminum compound, a cycloolefin addition polymer havingsubstantially no compositional distribution is obtained.

According to the present invention, furthermore, especially whencycloolefin monomers are polymerized using a multi-component catalystcomprising (a) a palladium compound, (b-2) an addition complex of aspecific phosphine compound and an organoaluminum compound and (c) anionic boron compound or the like, addition (co)polymerization of thecycloolefin compounds can be carried out with high polymerizationactivity, and a cycloolefin addition polymer can be produced with highproductivity. Moreover, even when a trace amount of oxygen is present inthe polymerization system, influence on the polymerization activity issmall, and even when a monomer composition containing a cycloolefincompound having a polar group, particularly a hydrolyzable silyl group,is copolymerized, addition copolymerization can be carried out with highpolymerization activity.

EXAMPLES

The present invention is further described with reference to thefollowing examples, but it should be construed that the invention is inno way limited to those examples.

In the following examples, molecular weight, total light transmittance,glass transition temperature, tensile strength/elongation, andrandomness in the copolymerization reaction are measured or evaluated bythe methods described below.

(1) Molecular Weight

The molecular weight was measured at 120° C. by means of a WATERS 150CModel gel permeation chromatography (GPC) apparatus using a TOSOH H typecolumn and using o-dichlorobenzene as a solvent. The resulting molecularweight is a value in terms of standard polystyrene.

(2) Total Light Transmittance

A film having a thickness of about 150 μm was formed, and a total lighttransmittance of the film was measured in accordance with ASTM-D1003.

(3) Glass Transition Temperature

The glass transition temperature was determined as a peak temperature oftemperature dispersion of Tan δ (ratio of a loss elastic modulus E″ to astorage elastic modulus E′, Tan δ=E″/E′) that is measured as a dynamicviscoelasticity. In the measurement of the dynamic viscoelasticity, apeak temperature of Tan δ was measured using Rheovibron DDV-01FP(manufactured by Orientec Co., Ltd.) and using a member having ameasuring frequency of 10 Hz, a heating rate of 4° C./min, a vibrationexcitation mode of a single wave form and a vibration excitationamplitude of 2.5 μm.

(4) Coefficient of Linear Expansion

A piece of a film having a test shape of about 150 μm thickness, 10 mmlength and 10 mm width was fixed upright in TMA (Thermal MechanicalAnalysis) SS6100 (manufactured by Seiko Instruments Inc.). To the film,a load of 1 g was applied by means of a probe, and in order to removeheat history of the film, the temperature was temporarily raised up to200° C. from room temperature at a rate of 5° C./min. Then, thetemperature was again raised from room temperature at a rate of 5°C./min, and from an inclination of extension of the film between 50° C.and 150° C., a coefficient of linear expansion was determined.

(5) Tensile Strength/Elongation

The tensile strength and elongation of a test specimen were measured ata pulling rate of 3 mm/min in accordance with JIS-K7113.

(6) Amount of Residual Solvent

A sample was placed in a hot air oven at 200° C. for 3 hours, and from achange in weight of the sample between before and after placing thesample in the oven, an amount of the residual solvent was determined.

(7) Compositional Analysis of Polymer in Copolymerization Reaction

Copolymerization reaction of the “specific monomer (1)” with the“specific monomer (2)” was carried out, and the polymerization wasterminated using isopropyl alcohol when the conversion of the monomersto a polymer was not higher than 20%. Then, an alkoxysilyl group, anester group and an oxetane group in the resulting polymer were measuredby a ¹H-NMR (solvent: C₆D₅) apparatus of 270 MHz to determine contentsof those groups in the resulting polymer.

Regarding the methoxy group, absorption (CH₃ of SiOCH₃) at 3.5 ppm wasused, and regarding the ethoxy group, absorption (CH₂ of SiOCH₂CH₃) at3.9 ppm was used. Regarding the methyl ester group, absorption(—C(O)OCH₃) at 3.5 ppm was used, and regarding the ethyl ester group,absorption (CH₂ of —C(O)OCH₂CH₃) at 3.9 ppm was used. Regarding theoxetanyl group, absorption (CH₂ adjacent to O atom of 4-member ring) at4.2-4.6 ppm was used.

When property absorptions of ¹H-NMR overlapped, the residual monomer inthe polymer solution was analyzed by a gas chromatogram to determine theamount introduced into the copolymer.

As an indication of randomness, a ratio (r) of a proportion (R_(p)) ofstructural units derived from the “specific monomer (2)” in the polymerto a proportion (R_(m)) of the “specific monomer (2)” in all of themonomers was calculated.r=R _(p) /R _(m)

As r comes near to 1, the randomness becomes better.

As r is farther away from 1 under the condition of r<1 or r>1, therandomness becomes worse.

Example 1

A 100 ml glass pressure bottle was charged with 30.7 g of dehydratedtoluene having a water content of 6 ppm, 30.7 g of cyclohexane, 79 g(7.0 mmol) of 5-triethoxysilylbicyclo[2.2.1]hept-2-ene and 8.75 g (93mmol) of bicyclo[2.2.1]hept-2-ene, and the charge opening was sealedwith a crown rubber cap. Then, 30 ml of ethylene in the form of a gaswas fed to the pressure bottle through the rubber cap.

The pressure bottle containing the solvent and the monomers was heatedto 75° C., and palladium 2-ethylhexanoate (0.00133 mg atom in terms ofPd atom), 0.00133 mmol of tricylohexylphosphoniumpentafluorophenylborate and 0.00667 mmol of triethylaluminum were addedin this order to initiate polymerization.

After 15 minutes from the initiation of polymerization, a part of thepolymer solution was sampled from the polymerization system. From thesolid content in the polymer solution sample, a conversion of themonomers to the polymer was determined, and from ¹H-NMR of 270 MHz, aproportion of structural units derived from the5-triethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer was determined.The conversion was 19%, the proportion of structural units derived fromthe 5-triethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer was 11% bymol, and the indication r of randomness was 1.6.

Although the polymerization reaction was carried out at 75° C. for 3hours, the polymer solution did not become turbid and was transparent.To the solution was added 1 ml of dimethylaminoethanol to terminate thepolymerization. From the measurement of a solid content in the polymersolution, the conversion to the polymer proved to be 96%.

Operation of extraction removal of a catalyst residue from the polymersolution by the use of isopropanol containing lactic acid water wascarried out twice, and the polymer solution was introduced into 2 litersof isopropanol to solidify a polymer. After the solidification, thepolymer was dried at 80° C. for 17 hours under reduced pressure toobtain a polymer A.

A proportion of structural units derived from the5-triethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer A was determinedfrom ¹H-NMR of 270 MHz. The proportion of structural units derived fromthe 5-triethoxysilylbicyclo[2.2.1]hept-2-ene was 6.7% by mol. Thepolymer had a number-average molecular weight (Mn) of 74,000, aweight-average molecular weight (Mw) of 185,000 and a glass transitiontemperature (Tg) of 360° C.

Example 2

Polymerization was carried out in the same manner as in Example 1,except that 0.00133 mmol of tricyclohexylphosphonium-2-ethylhexanoateand 0.00133 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)boratewere used instead of 0.00133 mmol of tricyclohexylphosphoniumpentafluorophenylborate.

The conversion after 12 minutes from the initiation of polymerizationwas 18%, and the proportion of structural units derived from the5-triethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer was 12% by mol.The polymerization system did not become turbid until the polymerizationof 3 hours was completed, and the conversion to the polymer was 97%.

The polymer B obtained as above had a number-average molecular weight(Mn) of 63,000, a weight-average molecular weight (Mw) of 167,000 and aglass transition temperature (Tg) of 365° C. The proportion ofstructural units derived from the5-triethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer B was 6.8% bymol, and the indication r of randomness was 1.7.

Example 3

Polymerization was carried out in the same manner as in Example 1,except that 90 mmol of bicyclo[2.2.1]hept-2-ene and 10 mmol of5-trimethoxysilylbicyclo[2.2.1]hept-2-ene were used instead of 93 mmolof bicyclo[2.2.1]hept-2-ene and 7 mmol of5-triethoxysilylbicyclo[2.2.1]hept-2-ene.

The conversion after 15 minutes from the initiation of polymerizationwas 18%, and the proportion of structural units derived from the5-trimethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer was 15% by mol.The polymerization system did not become turbid until the polymerizationof 3 hours was completed, and the conversion to the polymer was 95%.

The polymer C obtained as above had a number-average molecular weight(Mn) of 72,000, a weight-average molecular weight (Mw) of 177,000 and aglass transition temperature (Tg) of 360° C. The proportion ofstructural units derived from the5-trimethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer C was 9.7% bymol, and the indication r of randomness was 1.5.

Example 4

Polymerization was carried out in the same manner as in Example 3,except that 10 mmol of methyl4-methyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-9-ene-4-carboxylate wasused instead of 10 mmol of 5-trimethoxysilylbicyclo[2.2.1]hept-2-ene.

The conversion after 20 minutes from the initiation of polymerizationwas 19%, and the proportion of structural units derived from the methyl4-methyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-9-ene-4-carboxylate inthe polymer was 6% by mol. The polymerization system did not becometurbid until the polymerization of 3 hours was completed, and theconversion to the polymer was 91%.

The polymer D obtained as above had a number-average molecular weight(Mn) of 62,000, a weight-average molecular weight (Mw) of 156,000 and aglass transition temperature (Tg) of 360° C. The proportion ofstructural units derived from the methyl4-methyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-9-ene-4-carboxylate inthe polymer D was 9.2% by mol, and the indication r of randomness was0.6.

Example 5

Polymerization was carried out in the same manner as in Example 2,except that 80 mmol of bicyclo[2.2.1]hept-2-ene and 20 mmol oftricyclo[5.2.1.0^(2,6)]dec-8-ene in which a proportion of the endo formwas 95% were used as monomers. From the analysis by a gas chromatogramof the residual monomers in the polymer solution, the proportion ofstructural units derived from the tricyclo[5.2.1.0^(2,6)]dec-8-ene inthe polymer proved to be 12% by mol. The copolymer solution did notbecome turbid until the polymerization of 3 hours was completed, and theconversion to the polymer was 92%.

The polymer E obtained as above had a number-average molecular weight(Mn) of 64,000, a weight-average molecular weight (Mw) of 177,000 and aglass transition temperature (Tg) of 365° C.

Comparative Example 1

Polymerization was attempted in the same manner as in Example 1, exceptthat tricyclophosphine was used instead of the tricyclohexylphosphoniumpentafluorophenylborate, but polymerization reaction did not take place.

Comparative Example 2

Polymerization was carried out in the same manner as in Example 2,except that tricyclohexylphosphine was used instead of thetricyclohexylphosphonium-2-ethyl-hexanoate.

The conversion after 12 minutes from the initiation of polymerizationwas 18%, and the proportion of structural units derived from the5-triethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer was 17% by mol.After 1 hour, the polymerization system began to become turbid, andafter 3 hours, the polymerization system was turbid and a gel-likepolymer was precipitated. The conversion to the polymer was 90%.

The polymer F obtained as above was soluble in p-chlorobenzene ando-dichlorobenzene. The polymer F had a number-average molecular weight(Mn) of 53,000, a weight-average molecular weight (Mw) of 187,000 and aglass transition temperature (Tg) of 365° C. The proportion ofstructural units derived from the5-triethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer F was 6.8% bymol, and the indication r of randomness was 2.4.

Reference Example 1

In a mixed solvent of 10 ml of methylcyclohexane and 40 ml of xylene, 10g of the polymer. A was dissolved. To the resulting solution,pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]and tris(2,4-di-t-butylphenyl)phosphite were added as antioxidants in aneach amount of 0.6 part by weight based on 100 parts by weight of thepolymer, and tributyl phosphite was added as a crosslinking agent in anamount of 1.4 parts by weight based on 100 parts by weight of thepolymer.

The polymer solution was filtered through a membrane filter having apore diameter of 10 μm to remove foreign matters and then cast on apolyester film at 25° C. The ambient temperature was slowly raised up to50° C. to remove the mixed solvent, whereby a film was formed.

After the amount of the residual solvent in the film became 5 to 10% byweight, the film was exposed to steam at 180° C. for 2 hours to preparea crosslinked film. Then, the film was exposed to a methylene chloridevapor atmosphere at 25° C. for 30 minutes to remove the residualsolvent. Thereafter, the film was vacuum dried at 80° C. for 30 minutesto remove methylene chloride to form a crosslinked film A-1 having athickness of 150 μm. The amount of the residual solvent in the resultingfilm A-1 was not more than 0.3% by weight. The evaluation results areset forth in Table 1.

Reference Example 2

A crosslinked film B-1 having a thickness of 150 μm was obtained in thesame manner as in Reference Example 1, except that the polymer B wasused instead of the polymer A. The amount of the residual solvent in theresulting film B-1 was not more than 0.3% by weight. The evaluationresults are set forth in Table 1.

Reference Example 3

A crosslinked film C-1 having a thickness of 150 μm was obtained in thesame manner as in Reference Example 1, except that the polymer C wasused instead of the polymer A. The amount of the residual solvent in theresulting film C-1 was not more than 0.3% by weight. The evaluationresults are set forth in Table 1.

Reference Example 4

Film formation was carried out in the same manner as in ReferenceExample 1, except that the polymer D was used instead of the polymer A.As a result, a partially crosslinked film D-1 having a thickness of 150μm was obtained. The amount of the residual solvent in the resultingfilm D-1 was not more than 0.3% by weight. The evaluation results areset forth in Table 1.

Comparative Reference Example 1

Film formation was carried out in the same manner as in ReferenceExample 1, except that the polymer E was used instead of the polymer A.As a result, a film E-1 having a thickness of 150 μm was obtained. Theamount of the residual solvent in the resulting film E-1 was not morethan 0.3% by weight. The evaluation results are set forth in Table 1.Because any hydrolyzable silyl group participating in crosslinking wasnot present in the polymer E, it is thought that the resulting film E-1was not crosslinked.

Comparative Reference Example 2

A crosslinked film F-1 having a thickness of 150 μm was obtained in thesame manner as in Reference Example 1, except that the polymer F wasused instead of the polymer A and the cast solvent was replaced withp-chlorobenzene. The amount of the residual solvent in the resultingfilm F-1 was not more than 0.3% by weight. The evaluation results areset forth in Table 1. TABLE 1 Coefficient Total light Tensile of linearFilm transmittance strength Elongation expansion No. (%) (MPa) (%)(ppm/° C.) Ref. Ex. 1 A-1 91 61 6.5 41 Ref. Ex. 2 B-1 91 60 6.3 41 Ref.Ex. 3 C-1 91 62 6.0 40 Ref. Ex. 4 D-1 91 61 6.2 40 Comp. Ref. E-1 91 556.8 53 Ex. 1 Comp. Ref. F-1 88 56 5.2 45 Ex. 2

Reference Example 5

In a 50 ml flask, 1.0 g of (3.57 mmol) of tricyclohexylphosphine wasdissolved in 10 ml of deuterated benzene in a nitrogen atmosphere toprepare a solution of 0.357 mmol/ml.

A ³¹P-NMR (nuclear magnetic resonance) spectrum of thetricyclohexylphosphine was measured by a JASCO Corporation JEOL-270Model nuclear magnetic resonance (NMR) apparatus using trimethylphosphite (140 ppm) as an external standard.

As a result, an absorption spectrum of the tricyclohexylphosphine wasobserved at 9.2 ppm.

Reference Example 6

A part of the deuterated benzene solution of Reference Example 5 waswithdrawn into a different flask, and air was fed in an amount of 1 mmolin terms of oxygen atom based on 1 mmol of the tricyclohexylphosphine tocontact them at 25° C. for 2 days. A ³¹P-NMR spectrum of thetricyclohexylphosphine solution having been contacted with air wasmeasured. As a result, there was no absorption spectrum of thetricyclohexylphosphine at 9.2 ppm, but an absorption spectrum oftricyclohexylphosphine oxide was newly observed at 45.7 ppm.

Reference Example 7

A part of the deuterated benzene solution of Reference Example 5 waswithdrawn into a different flask, then triethylaluminum was added in anamount of 1 mmol based on 1 mmol of the tricyclohexylphosphine, and theywere reacted at 25° C. for 30 minutes to synthesize an addition complexin the deuterated benzene.

A ³¹P-NMR spectrum of the complex solution of tricyclohexylphosphine andtriethylaluminum having a molar ratio of 1:1 was measured. As a result,there was no absorption spectrum of the tricyclohexylphosphine at 9.2ppm, but an absorption spectrum of an addition complex oftricyclohexylphosphine and triethylaluminum was newly observed at −4.0ppm.

Reference Example 8

Contact with air was carried out in the same manner as in ReferenceExample 6, except that a complex of tricyclohexylphosphine andtriethylaluminum having a molar ratio of 1:1 was used instead of thetricyclohexylphosphine.

Reference Example 9

An addition complex of cyclohexylphosphine and diethylaluminum chloridehaving a molar ratio of 1:1 was synthesized in the same manner as inReference Example 7, except that diethylaluminum chloride was usedinstead of the triethylaluminum.

Example 6

A 100 ml glass pressure bottle was charged with 9.4 g of dehydratedtoluene having a water content of 6 ppm, 37.6 g of cyclohexane having awater content of 5 ppm, 10 mmol of9-trimethoxysilyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene and 90mmol of bicyclo[2.2.1]hept-2-ene in a nitrogen atmosphere, and thecharge opening was sealed with a crown rubber cap. Then, 30 ml ofethylene of 0.1 MPa in the form of a gas was fed as a molecular weightmodifier to the pressure bottle through the rubber cap.

The pressure bottle containing the solvent and the monomers was heatedto 75° C., and 2×10⁻⁴ mg atom (in terms of Pd atom) of palladiumacetate, 2×10⁻⁴ mmol of the addition complex of tricyclohexylphosphineand triethylaluminum having a molar ratio of 1:1 obtained in ReferenceExample 7 and 2.4×10⁻⁴ mmol of triphenylcarbeniumtetrakispentafluorophenylborate [Ph₃C.B(C₆F₆)₄] were added in this orderto initiate polymerization.

Although the polymerization reaction was carried out at 75° C. for 3hours, the polymer solution did not become turbid and was transparent.To the solution was added 0.1 mmol of triethylsilane to terminate thepolymerization. From the measurement of a solid content in the polymersolution, the conversion to the polymer proved to be 95%.

Operation of extraction removal of a catalyst residue by adding 30 ml ofwater containing 1.0 mmol of triethanolamine to the polymer solution wascarried out twice, and the polymer solution was introduced into 2 litersof isopropanol to solidify a polymer. After the solidification, thepolymer was dried at 90° C. for 17 hours under reduced pressure toobtain a polymer G. The amounts of the residual metals in the polymer Gwere measured by atomic absorption analysis. As a result, the amount ofthe residual Pd atom was 0.5 ppm, and the amount of the residual Al atomwas 1.5 ppm.

Further, a proportion of structural units derived from the9-trimethoxysilyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene in thepolymer G was determined from ¹H-NMR of 270 MHz. As a result, theproportion of structural units derived from the9-trimethoxysilyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene was 9.7%by mol. The polymer had a number-average molecular weight (Mn) of74,000, a weight-average molecular weight (Mw) of 185,000 and a glasstransition temperature (Tg) of 360° C.

Example 7

Polymerization was carried out in the same manner as in Example 6,except that the addition complex of Reference Example 8 that had beencontacted with air was used instead of the addition complex oftricyclohexylphosphine and triethylaluminum obtained in ReferenceExample 7.

The conversion to the polymer was 97%.

The polymer H obtained as above had a number-average molecular weight(Mn) of 73,000, a weight-average molecular weight (Mw) of 187,000 and aglass transition temperature (Tg) of 365° C. The proportion ofstructural units derived from the5-triethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer H was 9.8% bymol.

Example 8

Polymerization was carried out in the same manner as in Example 6,except that subsequently to the addition of triphenylcarbeniumtetrakispentafluorophenylborate [Ph₃C.B(C₆F₆)₄] as a catalyst component,10×10⁻⁴ mmol of triethylaluminum was added, and 10 mmol of5-trimethoxysilylbicyclo[2.2.1]hept-2-ene was used instead of 10 mmol of9-trimethoxysilyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene in such amanner that addition of 5.0 mmol was carried out prior to thepolymerization and thereafter addition of 1.0 mmol was carried out 5times at intervals of 20 minutes.

The polymerization system did not become turbid until the polymerizationof 3 hours was completed, and the conversion to the polymer was 98%.

The polymer I obtained as above had a number-average molecular weight(Mn) of 72,000, a weight-average molecular weight (Mw) of 177,000 and aglass transition temperature (Tg) of 360° C. The proportion ofstructural units derived from the5-trimethoxysilylbicyclo[2.2.1]hept-2-ene in the polymer I was 9.7% bymol.

A 20 wt % p-xylene solution of the polymer I was prepared and subjectedto solution casting (casting method). As a result, an opticallytransparent film was obtained. Further, a film to which cyclohexylp-toluenesulfonate had been added was crosslinked using steam, and as aresult, a transparent crosslinked film having excellent chemicalresistance and solvent resistance was obtained.

Example 9

Polymerization was carried out in the same manner as in Example 6,except that 10 mmol of methyl4-methyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-9-ene-4-carboxylate wasused instead of 10 mmol of9-trimethoxysilyltetracyclo[6.2.1.1^(3,6)0^(2,7)]dodec-4-ene.

The polymerization system did not become turbid until the polymerizationof 3 hours was completed, and the conversion to the polymer was 91%.

The polymer J obtained as above had a number-average molecular weight(Mn) of 62,000, a weight-average molecular weight (Mw) of 156,000 and aglass transition temperature (Tg) of 360° C. The proportion ofstructural units derived from the methyl4-methyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-9-ene-4-carboxylate inthe polymer J was 9.2% by mol.

Example 10

A 100 ml glass pressure bottle was charged with 37.6 g of cyclohexane asa solvent, 9.4 g of toluene as a solvent, 97 mmol ofbicyclo[2.2.1]hept-2-ene as a monomer and also as a cycloolefin, 3 mmolof 9-trimethoxysilyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene as amonomer and 10×10⁻⁴ mmol of cycloocta-1,4-diene as a cyclicnon-conjugated diene, and then further charged with 10×10⁻⁴ mmol oftriethylaluminum and 1.4×10⁻⁴ mmol of tricyclohexylphosphine. Then, thecharge opening was sealed with a crown rubber cap, and formation of anaddition complex of triethylaluminum and cyclohexylphosphine was carriedout at 30° C. for 10 minutes. Thereafter, 30 ml of ethylene of 0.1 MPain the form of a gas was fed as a molecular weight modifier, andfurther, 2×10⁻⁴ mmol (in terms of Pd atom) of palladium acetate and2.4×10⁻⁴ mmol of triphenylcarbenium tetrakispentafluorophenylborate[Ph₃C.B(C₆F₆)₄] were fed to initiate polymerization at 75° C.

The polymer solution after 3 hours from the initiation of polymerizationwas transparent, and the conversion to the polymer was 99%. The polymerwas solidified by the use of isopropanol and then dried to obtain apolymer K.

The polymer K obtained as above had a number-average molecular weight(Mn) of 64,000 and a weight-average molecular weight (Mw) of 177,000.The proportion of structural units derived from the9-trimethoxysilyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene in thepolymer K was 3.0% by mol, and the glass transition temperature (Tg) was375° C.

Example 11

Polymerization was carried out in the same manner as in Example 6,except that 100 mmol of 5-n-hexylbicyclo[2.2.1]hept-2-ene (endo form/exoform ratio=20/80) was used as a monomer, 1.5×10⁻⁴ mmol of the additioncomplex of tricyclohexylphosphine and diethylaluminum chloride having amolar ratio of 1:1 obtained in Reference Example 9 was used as acatalyst component instead of the addition complex oftricyclohexylphosphine and triethylaluminum having a molar ratio of 1:1.

The conversion to the polymer after 1.5 hours from the initiation ofpolymerization was 82%. The polymerization was terminated to obtain apolymer L.

The polymer solution was transparent, and a film obtained from a 20 wt %cyclohexane solution of the polymer L by solution casting was alsotransparent.

Example 12

A 100 ml glass pressure bottle was charged with 9.4 g of dehydratedtoluene having a water content of 6 ppm, 37.6 g of cyclohexane having awater content of 5 ppm, 10 mmol of9-trimethoxysilyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene and 90mmol of bicyclo[2.2.1]hept-2-ene in a nitrogen atmosphere, and thecharge opening was sealed with a crown rubber cap. Then, 35 ml ofethylene in the form of a gas was fed to the pressure bottle through therubber cap.

A catalyst previously prepared by aging 3×10⁻⁴ mg atom (in terms of Pdatom) of palladium bis(acetylacetonate), 3×10⁻⁴ mmol of the additioncomplex of tricyclohexylphosphine and triethylaluminum having a molarratio of 1:1 obtained in Reference Example 7, 3.4×10⁻⁴ mmol oftriphenylcarbenium tetrakispentafluorophenylborate [Ph₃C.B(C₆F₆)₄] and15×10⁻⁴ mmol of bicyclo[2.2.1]hepta-2,5-diene in 2 ml of toluene as asolvent at 60° C. for 30 minutes was placed in the pressure bottlecontaining the solvent and the monomers and having been heated to 75°C., to initiate polymerization.

Although the polymerization reaction was carried out at 75° C. for 3hours, the polymer solution did not become turbid and was transparent.To the solution was added 1 ml of dimethylaminoethanol to terminate thepolymerization. From the measurement of a solid content in the polymersolution, the conversion to the polymer proved to be 92%.

The proportion of structural units derived from the9-trimethoxysilyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene in theresulting polymer M was 9.6% by mol

The polymer M had a number-average molecular weight (Mn) of 48,000 and aweight-average molecular weight (Mw) of 235,000, and had a little widemolecular weight distribution.

Example 13

Polymerization was carried out in the same manner as in Example 6,except that after the addition of 30 ml of ethylene in the form of agas, 30 ml of air was further added to the pressure bottle. Theconversion to the polymer after 3 hours from the initiation ofpolymerization was 96%.

The proportion of structural units derived from the9-trimethoxysilyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene in theresulting polymer N was 9.8% by mol.

The polymer N had a number-average molecular weight (Mn) of 76,000 and aweight-average molecular weight (Mw) of 187,000.

In comparison with Example 6, it was found that addition of air to thepolymerization system exerted no influence on the polymerizationactivity and the molecular weight.

Comparative Example 3

Polymerization was carried out in the same manner as in Example 6,except that 2.0×10⁻⁴ mmol of tricyclohexylphosphine was used instead of2.0×10⁻⁴ mmol of the addition complex of tricyclohexylphosphine andtriethylaluminum having a molar ratio of 1:1.

The conversion to the polymer after 3 hours from the initiation ofpolymerization was 95%.

Comparative Example 4

Polymerization was carried out in the same manner as in Example 6,except that 2.0×10⁻⁴ mmol of the tricyclohexylphosphine prepared inReference Example 6, which had been contacted with air, was used insteadof 2.0×10⁻⁴ mmol of the addition complex of tricyclohexylphosphine andtriethylaluminum having a molar ratio of 1:1.

The conversion to the polymer after 3 hours from the initiation ofpolymerization was 0%.

Comparative Example 5

Polymerization was carried out in the same manner as in Example 13,except that 2.0×10⁻⁴ mmol of tricyclohexylphosphine was used instead of2.0×10⁻⁴ mmol of the addition complex of tricyclohexylphosphine andtriethylaluminum having a molar ratio of 1:1.

The conversion to the polymer after 3 hours from the initiation of thepolymerization was 65%, and the conversion to the polymer after 7 hourswas 78%.

The proportion of structural units derived from the9-trimethoxysilyltetracyclo[6.2.1.1^(3,6).0^(2,7)]dodec-4-ene in theresulting polymer was 9.8% by mol. The polymer had a number-averagemolecular weight (Mn) of 56,000 and a weight-average molecular weight(Mw) of 137,000.

In comparison with Example 6 and Example 13, it was found that additionof air to the polymerization system caused lowering of polymerizationactivity and lowering of molecular weight.

INDUSTRIAL APPLICABILITY

The cycloolefin addition polymer obtained by the invention can be usednot only for optical materials but also for electronic/electric parts,medical equipment materials, electrical insulating materials andpackaging materials.

Examples of the optical materials for which the cycloolefin additionpolymer is employable include light guide plates, protective films,deflection films, phase difference films, touch panels, transparentelectrode substrates, optical recording substrates, such as CD, MD andDVD, optical lenses, and sealing materials.

Examples of the electronic/electric parts for which the cycloolefinaddition polymer is employable include liquid crystal elements, liquidcrystal substrates, containers, trays, carrier tapes, separation films,cleaning containers, pipes, and tubes.

Examples of the medical equipment materials for which the cycloolefinaddition polymer is employable include medicine containers, ampoules,syringes, infusion fluid bags, sample containers, test tubes,blood-collecting tubes, sterilizing containers, pipes, and tubes.

Examples of the electrical insulating materials for which thecycloolefin addition polymer is employable include coating materials ofelectrical wires and cables, insulating materials of OA machines such ascomputer, printer and copy machine, and insulating materials of printedboards.

1. A process for producing a cycloolefin addition polymer, comprisingaddition-polymerizing one or more cycloolefin monomers comprising acycloolefin compound represented by formula (1), in the presence of amulti-component catalysts comprising: (a) a palladium compound, and (b)one or more phosphorus compounds selected from the group consisting ofcompounds (b-1) and (b-2): wherein (b-1) comprises a phosphonium saltrepresented by formula (b1)[PR²R³R⁴R⁵]⁺[CA₁]⁻   (b1) wherein P is a phosphorus atom, R² is asubstituent selected from the group consisting of a hydrogen atom, analkyl group of 1 to 20 carbon atoms, a cycloalkyl group and an arylgroup, R³ to R⁵ are each independently a substituent selected from thegroup consisting of an alkyl group of 1 to 20 carbon atoms, a cycloalkylgroup and an aryl group, and [CA₁]⁻ is a counter anion selected from thegroup consisting of a carboxylic acid anion, a sulfonic acid anion and asuperstrong acid anion comprising an atom selected from the groupconsisting of B, P Sb and F, wherein (b-2) comprises an addition complexof a phosphine compound that comprises a substituent selected from thegroup consisting of an alkyl group of 3 to 15 carbon atoms, a cycloalkylgroup and an aryl group, wherein the addition complex has a cone angle(θ deg) of 170 to 200, and an organoaluminum compound;

wherein A¹ to A⁴ are each independently selected from the groupconsisting of a hydrogen atom, a halogen atom, an alkyl group of 1 to 15carbon atoms, a cycloalkyl group, an aryl group, an ester group, anoxetanyl group, an alkoxy group, a trialkylsilyl group and a hydroxylgroup, wherein A¹ to A⁴ may be each bonded to a cyclic structure througha bond group of 0 to 10 carbon atoms, wherein said bond group isselected from the group consisting of an alkylene group of 1 to 20carbon atoms, an oxygen atom, a nitrogen atom and a sulfur atom, whereinA¹ and A² may form an alkylidene group comprising 1 to 5 carbon atoms, asubstituted or unsubstituted alicyclic or aromatic ring of comprising 5to 20 carbon atoms or a heterocyclic ring of comprising 2 to 20 carbonatoms, wherein A¹ and A³ may form a substituted or unsubstitutedalicyclic or aromatic ring comprising 5 to 20 carbon atoms or aheterocyclic ring comprising 2 to 20 carbon atoms, and wherein m is 0 or1: to form the cycloolefin addition polymer.
 2. The process forproducing a cycloolefin addition polymer as claimed in claim 1, whereinthe multi-component catalyst further comprises, in addition to thecomponent (a) and the component (b-1), (c) a compound selected from thegroup consisting of an ionic boron compound, an ionic aluminum compound,an aluminum compound of Lewis acidity and a boron compound of Lewisacidity.
 3. The process for producing a cycloolefin addition polymer asclaimed in claim 1, wherein the multi-component catalyst furthercomprises, in addition to the component (a) and the component (b-2), (d)an organoaluminum compound.
 4. The process for producing a cycloolefinaddition polymer as claimed in claim 3, wherein the content of theorganoaluminum compound (d) is in the range of 0.1 to 200 mol based on 1gram atom of palladium of the palladium compound (a).
 5. The process forproducing a cycloolefin addition polymer as claimed in claim 1, whereinthe palladium compound (a) is an organic carboxylate of palladium or aβ-diketone compound of palladium.
 6. The process for producing acycloolefin addition polymer as claimed in claim 1, wherein themulti-component catalyst is a catalyst prepared in the presence of atleast one compound selected from the group consisting of a polycyclicmonoolefin comprising a bicyclo[2.2.1]hept-2-ene structure, anon-conjugated diene comprising a bicycle[2.2.1]hept-2-ene structure, amonocyclic non-conjugated diene, a straight-chain non-conjugated diene,and combinations thereof.
 7. The process for producing a cycloolefinaddition polymer as claimed in claim 1, wherein the multi-componentcatalyst is a catalyst prepared in the presence ofbicyclo[2.2.1]hept-2-ene, a bicyclo[2.2.1]hept-2-ene derivativecomprising one or more hydrocarbon groups comprising 1 to 15 carbonatoms, or a combination thereof.
 8. The process for producing acycloolefin addition polymer as claimed in claim 1, wherein thecycloolefin monomers comprise a cycloolefin compound of formula (2)-1 orformula (2)-2:

wherein R¹ and R² are each a substituent selected from the groupconsisting of an alkyl group of 1 to 10 carbon atoms, a cycloalkyl groupand an aryl group, wherein X is selected from the group consisting of analkoxy group of 1 to 5 carbon atoms and a halogen atom, wherein Y is aresidue of a hydroxyl group of an aliphatic diol comprising 2 to 4carbon atoms, wherein k is an integer of 0 to 2, and n is 0 or
 1. 9. Theprocess for producing a cycloolefin addition polymer as claimed in claim8, wherein the cycloolefin compound of formula (2)-1 or formula (2)-2 isused in a total amount of 0.1 to 30% by mol in the whole amount of allthe cycloolefin monomers.
 10. The process for producing a cycloolefinaddition polymer as claimed in claim 1, wherein the cycloolefin monomerof formula (1) in which A¹ to A⁴ are each independently a hydrogen atomor a hydrocarbon group of 1 to 15 carbon atoms is used in an amount ofnot less than 50% by mol in the whole amount of all the cycloolefinmonomers.
 11. The process for producing a cycloolefin addition polymeras claimed in claim 2, wherein the multi-component catalyst furthercomprises, (d) an organoaluminum compound.
 12. The process for producinga cycloolefin addition polymer as claimed in claim 11, wherein thecontent of the organoaluminum compound (d) is in the range of 0.1 to 200mol based on 1 gram atom of palladium of the palladium compound (a). 13.The process for producing a cycloolefin addition polymer as claimed inclaim 2, wherein the palladium compound (a) is an organic carboxylate ofpalladium or a β-diketone compound of palladium.
 14. The process forproducing a cycloolefin addition polymer as claimed in claim 3, whereinthe palladium compound (a) is an organic carboxylate of palladium or aβ-diketone compound of palladium.
 15. The process for producing acycloolefin addition polymer as claimed in claim 4, wherein thepalladium compound (a) is an organic carboxylate of palladium or aβ-diketone compound of palladium.
 16. The process for producing acycloolefin addition polymer as claimed in claim 2, wherein themulti-component catalyst is a catalyst prepared in the presence of atleast one compound selected from the group consisting of a polycyclicmonoolefin comprising a bicyclo[2.2.1]hept-2-ene structure, anon-conjugated diene comprising a bicycle[2.2.1]hept-2-ene structure, amonocyclic non-conjugated diene, a straight-chain non-conjugated diene,and combinations thereof.
 17. The process for producing a cycloolefinaddition polymer as claimed in claim 3, wherein the multi-componentcatalyst is a catalyst prepared in the presence of at least one compoundselected from the group consisting of a polycyclic monoolefin comprisinga bicyclo[2.2.1]hept-2-ene structure, a non-conjugated diene comprisinga bicycle[2.2.1]hept-2-ene structure, a monocyclic non-conjugated diene,a straight-chain non-conjugated diene, and combinations thereof.
 18. Theprocess for producing a cycloolefin addition polymer as claimed in claim4, wherein the multi-component catalyst is a catalyst prepared in thepresence of at least one compound selected from the group consisting ofa polycyclic monoolefin comprising a bicyclo[2.2.1]hept-2-ene structure,a non-conjugated diene comprising a bicycle[2.2.1]hept-2-ene structure,a monocyclic non-conjugated diene, a straight-chain non-conjugateddiene, and combinations thereof.
 19. The process for producing acycloolefin addition polymer as claimed in claim 5, wherein themulti-component catalyst is a catalyst prepared in the presence of atleast one compound selected from the group consisting of a polycyclicmonoolefin comprising a bicyclo[2.2.1]hept-2-ene structure, anon-conjugated diene comprising a bicycle[2.2.1]hept-2-ene structure, amonocyclic non-conjugated diene, a straight-chain non-conjugated diene,and combinations thereof.
 20. The process for producing a cycloolefinaddition polymer as claimed in claim 2, wherein the multi-componentcatalyst is a catalyst prepared in the presence ofbicyclo[2.2.1]hept-2-ene, a bicyclo[2.2.1]hept-2-ene derivativecomprising one or more hydrocarbon groups comprising 1 to 15 carbonatoms, or a combination thereof.